EPA-600/2-74-003

March 1974
                       Environmental Protection Technology Series
   The Development of  Phosphate-Free


   Heavy  Duty Detergents
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                                Office of Research and Development


                                U.S. Environmental Protection Agency


                                Washington, D.C. 20460

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             RESEARCH REPORTING SERIES
Research reports of the  Office   of  Research  and
Monitoring,   Environmental Protection Agency, have
been grouped into five series.   These  five  broad
categories  were established to  facilitate further
development   and  application    of    environmental
technology.    Elimination  of traditional grouping
was  consciously  planned  to  foster   technology
transfer  and  a  maximum  interface  in  related
fields.   The five series are:

   1.  Environmental Health Effects Research
   2.  Environmental Protection  Technology
   3.  Ecological Research
   4.  Environmental Monitoring
   5.  Socioeconomic Environmental  Studies

This report  has been assigned to the ENVIRONMENTAL
PROTECTION   TECHNOLOGY   series.     This   series
describes   research   performed to  develop  and
demonstrate    instrumentation,    equipment    and
methodology   to  repair  or  prevent environmental
degradation  from point and  non-point  sources  of
pollution.   This work provides the  new or improved
technology  required for the control and treatment
of pollution sources to meet environmental quality
standards.
                    EPA REVIEW NOTICE
This report has been reviewed by the Office of  Research and
Development, EPA, and approved for publication.  Approval does
not signify that the contents necessarily reflect the views
and policies of the Environmental Protection Agency, nor does
mention of trade names or commercial products constitute
endorsement or recommendation for use.

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                                              EPA-600/2-74-003
                                              March 1974
   THE DEVELOPMENT  OF PHOSPHATE-FREE HEAVY DUTY

                     DETERGENTS
                         By

                Anthony M. Schwartz
                  A.  Eleanor Davis
                  Project 16080 FWE
               Program Element 1BB045
                   Project Officer

                   Dr. A. Forziati
           Office of Program Management
       U.S. Environmental Protection Agency
               Washington, D.C.  20460
                    Prepared  for

        OFFICE OF RESEARCH AND DEVELOPMENT
       U.S.  ENVIRONMENTAL PROTECTION AGENCY
               WASHINGTON, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office
            Washington, D.0.80408 - Price I2.W

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                                 ABSTRACT

 The purpose of this project was to demonstrate state-of-the-art possi-
 bilities for producing phosphate-free household laundry detergents of
 satisfactory environmental and performance characteristics.  The work
 involved formulation of several hundred experimental  detergent compo-
 sitions  using different surfactant-builder combinations.  These were
 tested for laundering performance, acceptability of physical form,
 biodegradability,  aquatic toxicity, potential  hazard  in use, and growth
 stimulation of algae.  Feasibility of economical production on an
 industrial scale was also considered.  Some partially satisfactory
 formulations were  arrived at,  their shortcomings being with regard
 to  performance and/or economic feasibility,  the two factors that must
 in  the immediate state-of-the-art  be traded off.  These formulations
 coincide remarkably with the formulations  developed independently
 by  the industry and offered in jurisdictions where phosphate-con-
 taining  detergents  are banned.   Some new builders and surfactant-
 builder  combinations showed considerable promise,  but could not be
 completely checked  out with regard to all  stipulated  characteristics.
 Further  work with these novel  materials is recommended,  but only
 along  environmental and health-hazard lines.
This report was  submitted  in fulfillment of  Project Number 16080 FWE
and Contract  Number  14-12-875 by Gillette  Research Institute under the
sponsorship of the Environmental Protection Agency.  Work was com-
pleted as of  November  30,  1973.

                                     ii

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                           TABLE OF CONTENTS


                                                                 Page

Abstract                                                          ii

List of Figures                                                   iv

List of Tables                                                    x

Acknowledgements                                                  xiii

Conclusions                                                       xiv

Recommendations                                                   xvii

Sections

Introduction                                                      1

Program Design                                                    4

Experimental                                                      15

Results   -                                                        26

Discussion                                                        45

Tables 1-13                                                     53

Figures 1-36                                                    89

Appendix A.  Test Methods, Non- Launder ing                         125

Appendix B.  Laundering Test Methods Development                  155

Tables BG1 - BG9                                                  174

Figures 37 - 49                                                   187

Appendix C.  Code List of Materials                               200

Appendix D.  Selected Recent Patents Relating to Phosphate-Free   210
             Household Laundering Detergents

Appendix E.  Chronic Aquatic Toxicity Tests                       223
                                  iii

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                           LIST OF FIGURES
Figure No.                      Title                            Page

   1.          Detergency v. concentration.   Item 20-147           89
               High titer soap.  Series ref.  210.
               Empa soil.  200 ppm water.

   2.          Detergency v. concentration.   Item 86-706.          90
               Soap-lime soap disperser.  Series ref.  210.
               Empa soil.  200 ppm water.

   3.          Detergency v. concentration.   Item 86-707.          91
               Soap-lime soap disperser.  Series ref.  210.
               Empa soil.  200 ppm water.

   4.          Detergency v. concentration.   Item 86-708.          92
               Soap-lime soap disperser.  Series ref.  210.
               Empa soil.  200 ppm water.

   5.          Detergency v. concentration.   Item 90-730           93
               anionic sulfonate.  Series  ref.  243.
               Colgate soil.  Tap water.  Blend fabric.

   6.          Detergency v. concentration.   Item 90-730           94
               anionic sulfonate.  Series  ref.  243.
               Colgate soil.  Tap water.  Cotton.

   7-          Detergency v. concentration.   IAS and Item          95
               90-730 anionic sulfonate.  Series ref.  239C.
               Colgate soil.  200 ppm water.  Blend  fabric.

   8.          Detergency v. concentration.   IAS and Item          96
               90-730 anionic sulfonate.  Series ref.  239C.
               Colgate soil.  200 ppm water.  Cotton.

   9.          Detergency v. concentration.   IAS and Item          97
               90-730 anionic sulfonate.  Series ref.  239.
               Spangler soil multicycle.  200 ppm water.
               Blend fabric.
                                  iv

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                      LIST OF FIGURES (Continued)

Figure No.                       Title                           Page

   10.         Detergency v.  concentration.   IAS  and Item         98
               90-730 anionic sulfonate.   Series  ref.  239.
               Spangler soil  multicycle.   200 ppm water.
               Cotton.

   11.         Detergency v.  concentration.   IAS  and IAS-         99
               CMOS (item 80-647) and Item 90-730 anionic
               sulfonate.  Series ref. 243.   Spangler soil
               multicycle. Tap water.  Blend fabric.

   12.         Detergency v.  concentration.   IAS  and IAS-         100
               CMOS (item 80-647) and Item 90-730 anionic
               sulfonate.  Series ref. 243.   Spangler soil
               multicycle. Tap water.  Cotton.

   13.         Detergency v.  concentration.   Items 42-350         101
               and 42-353 zwitterionic.  Series  ref. 247
               and 252 (for AATCCWOB).  Colgate  soil.
               200 ppm water.  Blend fabric.

   14.         Detergency v.  concentration.   Items 42-350         102
               and 42-353 zwitterionic.  Series  ref. 247
               and 252 (for AATCCWOB).  Colgate  soil.
               200 ppm water.  Cotton.

   15.         Detergency v.  concentration.   Items 104-856         103
               and 108-880 anionics.  Series  refs. 252
               (AATCGWOB) 250 and 256.  Colgate  soil.
               200 ppm water.  Blend fabric.

   16.         Detergency v.  concentration.   Items 104-856         104
               and 108-880 anionics.  Series  refs. 252
               (AATCCWOB) 250 and 256.  Colgate  soil.
               200 ppm water.  Cotton.

   17.         Detergency v.  concentration.   Items 104-855        105
               (detergent D)  and 96-782 (detergent E).
               Series refs. 252  (AATCCWOB) and 248.
               Colgate soil.   200 ppm water.   Blend fabric.

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                      LIST OF FIGURES (Continued)
Figure No.                       Title

   18.         Detergency v. concentration.  Items 104-855        106
               (detergent D) and 96-782 (detergent E).
               Series refs. 252 (AATCCWOB) and 248.
               Colgate soil.  200 ppm water.  Cotton.

   19.         Detergency v. concentration.  Items 104-855        107
               (detergent D) and 96-782 (detergent E).
               Series refs. 253 and 254.  Spangler multi-
               cycle.  200 ppm water.  Blend fabric.

   20.         Detergency v. concentration.  Items 104-855        108
               (detergent D) and 96-782 (detergent E).
               Series refs. 253 and 254.  Spangler multi-
               cycle.  200 ppm water.  Cotton.

   21.         Detergency v. concentration.  Items 96-783         109
               (detergent C) and 96-784 (detergent T).
               Series ref. 240.  Colgate soil.  200 ppm
               water.  Blend fabric.

   22.         Detergency v. concentration.  Items 96-783         110
               (detergent C) and 96-784 (detergent T).
               Series ref. 240.  C9lgate soil.  200 ppm
               water.  Cotton.

   23.         Detergency v. concentration.  Series ref.  259      111
               (AATCCWOB) 268 (HEIDA).  Colgate soil.
               200 ppm water.  Blend fabric.

   24.         Detergency v. concentration.  Series ref.  259      112
               (AATCCWOB) 268 (HEIDA).  Colgate soil.
               200 ppm water.  Cotton.

   25.         Detergency v. concentration.  Item 100-823.        113
               Series ref. 252 (AATCCWOB)  255 (item 100-823).
               Colgate soil.  200 ppm water.  Blend fabric.
                                   vi

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                      LIST OF FIGURES  (Continued)
Figure No.                        Title                           Page

   26.         Detergency y.  concentration.   Item 100-823.         114
               Series ref. 252  (AATCCWOB)  255 (item 100-823).
               Colgate soil.  200 ppm water.   Cotton.

   27.         Detergency v.  concentration.   Item 104-860.         115
               Series ref. 259  (AATCCWOB)  257 (item 104-860).
               Colgate soil.  200 ppm water.   Blend fabric.

   28.         Detergency v.  concentration.   Item 104-860.         116
               Series ref. 259  (AATCCWOB)  257 (item 104-860).
               Colgate soil.  200 ppm water.   Cotton.

   29.         Detergency v.  concentration.   Item 106-866.         117
               Series ref. 258,  259,  260.  Colgate soil.
               200 ppm water.  Blend  fabric.

   30.         Detergency v.  concentration.   Item 106-866.         118
               Refs.  258, 259,  260.   Colgate  soil.  200 ppm
               water.  Cotton.

   31.         Detergency v.  concentration.   Item 106-866.         119
               Series ref. 267.   Spangler  multicycle.
               200 ppm water.  Blend  fabric.

   32.         Detergency v.  concentration.   Item 106-866.         120
               Series ref. 267-   Spangler  multicycle.
               200 ppm water.  Cotton.

   33.         Detergency v.  concentration.   Item 80-647.          121
               Series ref. 243.   Colgate soil.  200 ppm water.
               Blend  fabric.

   34.         Detergency v.  concentration.   Item 80-647.          122
               Series ref. 243.   Colgate soil.  200 ppm water.
               Cotton.

   35.         Detergency v.  concentration.   Item 90-279.          123
               Series ref. 240.   Colgate soil.  200 ppm water.
               Blend  fabric.
                                   vii

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                      LIST OF FIGURES (Continued)
Figure No.                       Title                           Page

   36.         Detergency v. concentration.  Item 90-279.          124
               Series ref. 240.  Colgate soil.   200 ppm water.
               Cotton.

   37.         Fabric finish study.  Spangler multicycle.          187
               200 ppm water.  AATCCWOB 0.3%.  Cotton.

   38.         Fabric finish study.  Spangler multicycle.          188
               AATCCWOB 0.3%.  Dacron.

   39.         Fabric finish study.  Spangler multicycle.          189
               200 ppm water.  AATCCWOB 0.3%.  Blend fabric.

   40.         Fabric finish study.  Colgate soil.  200 ppm       190
               water.  AATCCWOB.  Cotton.  Green reflectance
               values.

   41.         Fabric finish study.  Colgate soil.  200 ppm       191
               water.  AATCCWOB.  Cotton.  Whiteness values.

   42.         Fabric finish study.  Colgate soil.  200 ppm       192
               water.  AATCCWOB.  Dacron.  Green reflectance
               values.

   43.         Fabric finish study.  Colgate soil.  200 ppm       193
               water.  AATCCWOB.  Dacron.  Whiteness values.

   44.         Fabric finish study.  Colgate soil.  200 ppm       194
               water.  AATCCWOB.  Blend fabric  (commercial
               permanent press finish).  Green  reflectance
               values.

   45.         Fabric finish study.  Colgate soil.  200 ppm       195
               water.  AATCCWOB.  Blend fabric  (commercial
               permanent press finish).  Whiteness values.

   46.         Chelation curves of typical  strong, high           196
               efficiency chelants, NTA and maleic acid
               telomer.
                                  viii

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                      LIST OF FIGURES (Continued)
Figure No.                       Title                           Page

   47.         Chelation curves of weak,  moderate efficiency      197
               chelants, Na citrate and CMOS.

   48.       ,  Low efficiency polymeric chelants.  Akzo 294-10    198
               moderately strong, POCNa moderately weak.

   49.         Effect of molecular weight on chelating behavior   199
               in polyacrylic acids (Calnox).   Akzo OS starch
               typical of low efficiency moderate strength poly-
               meric builders.
                                   ix

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                             LIST OF TABLES


Table No.                        Title                     .r,  ..Page

   1           Detergency of Surfactants without Builder          53

   la          Detergency of Surfactants without Builder          57

   2           Detergency of Surfactant - Carbonate For-          59
               mulations

   3           Detergency of Surfactant - NTA Formulations        60

   3a          Detergency of NTA - Alpha Olefin Sulfonate         61
               Formulation at Varying Water Hardness and
               Concentration

   4           Detergency of Surfactant - SAND Formulations       62

   5           Detergency of Surfactant - SHIM Formulations       63

   6           Detergency of Polymeric Builder - Surfactant       64
               Formulations

   6a          Detergency of Polymeric Builder - Surfactant       66
               Formulations
 . '              \
   7           Detergency of Monomeric Builder - Surfactant       70
               Formulations
                                                               >   ',
   la          Detergency of Monomeric Builder - Surfactant       74
               Formulations
                                                   , _- ;
   7b          Effect of Concentration on Whiteness of            75
               Soiled Swatches
                                                                 4
                                                                 t
   7c          Effect of Water Hardness on Whiteness-of           76
               Soiled Swatches
                                                                :->J
   8           Representative Drum-Drier Formulations of          77
               Satisfactory Character

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                       LIST OF TABLES (Continued)
Table No.                        Title                           Page

   8a          Representative Liquid Formulations of              78
               Satisfactory Character

   9           Stimulatory Effect on Growth of Algae              79

  10           Acute Aquatic Toxicity of Detergents and           82
               Their Ingredients

  ll           Estimation of Biodegradability of Materials        84
               Used in Detergent Formulations "

  12           Hazard Test Results.  Detergent Formulations       86

  12a          Identification of Formulations in Table 12         87

  13           Effect of Multiple Washings on Build Up of         88
               Impurities in Fabric
 BG1



 BG2
k.
 K


 BG2A



 BG3



 BG3A



 BG4



 BG4A
  Instrumental Reflectances  of Laundered
  Pillowcases  After Six Cycles in Bundle Test

  Tergotometer Soil Removal  Values
  Cotton,  0.2%, Tap Water

  Tergotometer Redepositlon  Values
  Cotton,  0.2%, Tap Water

  Tergotometer Soil Removal  Values
  Durapress,  .2%,  Tap Water

  Tergotometer Redeposition  Values
;  Durapress, 0.2%,  Tap Water

  Tergotometer Soil Removal  Values
  Cotton,  0.3%, Tap Water

  Tergotometer Redeposition  Values
  Cotton,  0.3%, Tap Water
174


175


176


177


178


179


180
                                   xi

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                       LIST OF TABLES  (Continued)


Table No.                        Title
BG5            Tergotometer Soil Removal Values                  181
               Durapress, 0.3%, Tap Water

BG5A           Tergotometer Redeposition Values                  182
               Durapress, 0.3%, Tap Water

BG6            Rankings of Detergents in Different               183
               Washing Procedures

BG7            Whiteness Rankings of Soiled Swatches             184
               in Procedures 1 and 2

BG8            Whiteness Rankings of Soiled Swatches             185
               in Procedures 3, 4 and 5

BG9            Whiteness Rankings of Soiled Swatches             186
               Detergents M and D in Procedures 3,
               4 and 5.
                                 xii

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                             ACKNOWLEDGEMENTS

The writers wish to acknowledge the invaluable assistance of the
project's staff, especially those whose responsibility extended over
the entire period of its performance:   Dr. Vera Usdin for biological
and biochemical aspects of the program; Mr. Julian Berch and
Mr. Abraham Fookson for chemical analysis and formulation;
Dr. Ruth Patrick and Dr. Arthur Scheier of the Academy of Natural
Sciences, Philadelphia, who supervised and conducted all the work on
aquatic toxicity.  We extend special thanks to the EPA staff members
who advised on and monitored the work; and finally to the many com-
panies in the detergent and chemical industries that generously con-
tributed materials and information for use in the program.
                                  .Xiii

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                               CONCLUSIONS

1.   The problem was to provide a phosphate-free heavy duty household
laundering detergent having the stipulated environmental properties
and consumer-acceptable laundering performance.  The most immediately
applicable technical solutions worked out in the course of this pro-
ject are as follows:
     a.   A detergent consisting essentially of a mixture of conven-
          tional surfactants substantially unbuilt, the surfactant
          content being in the range of 40% or higher, i.e., two or
          more times the surfactant content of current conventional
          phosphate-built detergents.  This detergent would be
          liquid in form.
     b.   A detergent consisting of about 25% conventional sur-
          factant and 20-40% of silicate or mixed silicate-carbonate
          as a builder.  The carbonate content of this mixture
          should not be higher than about 25%.  This detergent
          would be solid.
     c.   A detergent consisting of a mixture of conventional sur-
          factants or special surfactants of high washing power
          together with sodium citrate or citrate and silicate
          as the builder.  These detergents can be liquid or solid
          depending on the surfactant.
                                  xiv

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          It is of interest that detergents in all three of these
          classes have been developed by the industry and offered
          in the marketplace in jurisdictions where phosphate-
          built detergents are banned.
2.   Soap and soap-lime soap disperser combinations are not considered
to offer performance of the type to which detergent users are ac-
customed.  Even in moderately hard water a high concentration is
needed to provide good soil removal, and the build-up of residues
in the fabric can become objectionably high.
3.   From the performance point of view NTA is a satisfactory sub-
stitute for phosphate.  Its adoption in commercial product would ap-
pear to hinge on questions of possible hazard, outside the scope of
this project.
4.   The product beta hydroxyethyl iminodiacetic acid (abbreviated
SHIM or HEIDA) appears to be a very promising potential substitute
for phosphate.  It has high building power and passes the stipulated
tests for environmental acceptability.  It appears close to the FDA
and CPSC borderlines with regard to toxicity, and requires further
testing on this point.  It appears more suited to liquid than to
solid formulations.
5.   The product carboxymethyloxysuccinic acid (abbreviated CMOS)
is a potential substitute for phosphate.  In building power it is
somewhat stronger than citrate, particularly with the most widely
used surfactants, but not as strong as phosphate.  Environmentally
it appears acceptable.
                                  xv

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 6.   The  polymeric  product  POCNa, produced and offered In Germany
 as a substitute  for phosphate builder, appears to have some potential
 as a phosphate substitute.   It  is relatively weak in building power,
 however,  and  possibly too slow  in biodegradation.
 7.   Several  other  polymeric products appear to provide satisfactory
 building  action  and be  at least partially biodegradable.  Whether or
 not they  are  satisfactorily biodegradable has not yet been settled.
 8.   A  large  number of  patents  have recently issued and continue to
 issue on  phosphate-free detergents that purport to be environmentally
 acceptable.   Several of the patent examples have been partly investi-
 gated,  and some  show promise.
 9.   The  concept of laundering  with low concentrations of unbuilt,
 environmentally  acceptable,  non-hazardous surfactants, in water
 softened  by in-situ ion exchange resins, has been cursorily explored.
 It is proposed as a concept worthy of further investigation.
 10.  The  satisfactory replacement of current phosphate-built deter-
 gents by  environmentally acceptable non-hazardous phosphate-free
 detergents of substantially equal performance is a very difficult
 economic  problem as well as  a technical problem.  Technical an-
 swers appear  to  be  near realization, although the complete establish-
ment of environmental acceptability and lack of hazard is a long and
difficult task (cf. NTA).   The  necessity for a trade-off between
cost and  performance must be realized, since phosphate is a relatively
 inexpensive commodity.  Furthermore, the economic dislocations and
the time  involved in effecting  such a replacement would under the
best of circumstances be formidable.
                                 xvi

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                        RECOMMENDATIONS

In view of the findings of this project, summarized in the DISCUSSION
and CONCLUSIONS sections of this report, it is recommended that:
1.   Performance and/or sponsorship of experimental work directed
explicitly toward the formulation of phosphate-free detergents be
discontinued.  This relates especially to the measurement and im-
provement of laundering performance.
2.   The detergent industry and its suppliers be encouraged to
develop complete data on the environmental and hazard characteristics
of new non-phosphate detergent formulations and their essential
ingredients.
3.   Full cooperation in this endeavor be offered with regard to
stipulating the various characteristics and establishing test pro-
tocols and standards of acceptability for them.
                               xvii

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                             INTRODUCTION

When this project was started in the summer of 1970 essentially all of
the heavy duty household laundering detergents marketed in the U.S.A.
contained as a necessary ingredient a substantial proportion of sodium
tripolyphosphate.  The potential ecological hazards of this material
and other phosphorus compounds had been recognized, but no generally
acceptable phosphate-free laundering compositions had been developed
to the stage of commercial feasibility.  The objective of the project
accordingly was to formulate a phosphate-free heavy duty household
laundering detergent which would be:
a.   satisfactorily biodegradable.
b.   non-stimulating to undesirable algae.
c.   non-toxic to fish and representative lower organisms in fish food
     chains.
d.   safe to use and to have in the household.
e.   satisfactory to the consumer in its performance.
f.   economically feasible to produce and market on a scale comparable
     with that of currently used phosphate-containing detergents;
     i.e. industrially and commercially feasible.
This was intended essentially as a demonstration program.  The aim was
to find out if such a product could be made using known materials and
existing technology.  It was understood that there could be no compro-
mise with either the environment or product safety requirements
(items a-e).  These could be clearly defined in terms of test protocols,

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 and no inordinate difficulty was anticipated in reaching agreement on
 such protocols.  Industrial feasibility and satisfactory performance,
  .\     
 however,  are not so easily defined and agreed upon.  With regard to
 these items- the following stand was adopted.
 Industrial feasibility implies that raw materials are adequate and pro-
 duction process.es sufficiently developed to allow reasonably early pro-
 duction in the mi11ion-ton per year range.  Judgment of industrial
'feasibility is based partly on our knowledge of the chemical industry
and partly oji assurances of those offering the candidate materials.
 Commercial feasibility is based on two factors, cost and performance.
 Performance is in turn made up of a large number of sub-factors which
      
 the household consumer considers in making her final judgment of ac-
 ceptability.  These include not only soil removing power (the factor
 Usually weighted most heavily) but also convenience of physical form,
 rapid solubility at laundering temperatures, no adverse effects on fab-
 rics or washing machine, etc.   It is in the cost and performance factors
 where some flexibility is allowable (in fact, inevitable) and where
 trade-offs can be made.  Just  as there are several different types of
 commercially successful phosphate detergent, we visualized more than
 ome type  pf phosphate^-free detergent as being able to make a commercial
       '    '   .'''
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keep fully abreast of announced developments and follow up on any that
appeared meritorious.  We could thus be regarded not only as researchers
seeking to develop a new product but in a limited sense as surrogate
consumers assaying the suitability of products that might appear from
other sources.

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                             PROGRAM DESIGN

 A.    LIMITATIONS ON MATERIALS SELECTED
 To  be considered as candidate detergent ingredients (surfactant,  builder
 or  auxiliary)  the materials used in this program had to  meet  certain
 economic and commercial requirements relating to cost and availability.
 Furthermore, certain types of auxiliary ingredients have been excluded
 from the study entirely.  Among the more important items in this  latter
 category are enzymes,  bleaches (both peroxygen and chlorine types),
 brighteners, fabric softeners, emollients,  anti-tarnish,  anti-caking
 and anti-dusting agents.  The mission was to find a non-phosphate for-
 mulation that  performed like the phosphate-containing ones.   Phosphate
 contributes, along with the surfactant,  to true physical removal  of
 soil;  and therefore this was the key performance effect  we studied.
 Enzymes  and  bleaches remove soil by chemical rather than physical
 action.   Brighteners contribute only the appearance of soil removal.
 The other ingredients  are not only unrelated to soil removal  but  are
 unaffected by  the  presence or absence of phosphate.   Thus  the ingre-
 dients of interest in  this study were surfactants,  builders,  anti-
 redeposition agents, and any other materials (solvents,  inorganic de-
 tergents,  etc.)  that might contribute to physical  soil removal.
 The  economic requirements were somewhat  more difficult to  pinpoint.
As mentioned above,  it  was  not considered likely that a  replacement
 formulation  could  be found  equal;in cost efficiency to the phosphate

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detergents.  The objective was to minimize the sacrifice that would
have to be made in cost efficiency,  and to satisfactorily balance the
cost factor against the performance  factor.  The performance can be,
and was, measured in the laboratory  with some precision.  Costs are
more difficult to estimate unless one is actually in commerce, ready
to negotiate firm purchase and sales contracts.  They can be estimated
with reasonable closeness, however,  if the process of manufacture is
known, by extrapolation from raw material costs, or from present prices
if the material is now being made on a limited scale.  Almost as im-
portant as the cost is the potential availability of the candidate
material on a large scale.  Detergent phosphate is used at a rate of
well over one million tons per year, and detergent compositions at a
rate of over three million tons per  year.  The only materials considered
seriously were those that seemed potentially available in the million
ton per year range at a cost not too far removed from present deter-
gent component costs.
Cost is of special importance when considering the builder alone rather
than the whole detergent formulation.  Many surfactants (soap is pos-
sibly the best known example) can deliver good laundering performance
if used at sufficiently high concentration.  In such cases, the builder
must be less costly than the surfactant for a builder*-surf act ant combina-
tion to make economic sense.                          >
No formal limitation was placed on the source of the experimental mate-
rials.  Most of the surfactants were available as items of commerce,
although a few were submitted as development samples by established
surfactant manufacturers.  Most of the builders were in the category
of development samples from established chemical manufacturers.  A
very small proportion of the builders were synthesized in our  labora-
tories, in most instances to establish guidelines on the relationship

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 between chemical structure and detergent building  effect.   It was an
 explicit policy to avoid or at least minimize  the  use  of newly  synthe-
 sized compounds,  because the complete proving  of safety, performance
 and feasibility would take too long a time.  Primary attention  was
 given to materials about which such information was  available.

 B.    LIMITATIONS ON CONSUMER ACCEPTABILITY
 To  gain customer acceptance a detergent  product must meet certain re-
 quirements  with regard to physical form.   Suspensions  or emulsions that
 tend to settle  or break in the package are not considered acceptable.
 Powdered or beaded products that sinter  to a solid cake or  deliquesce
 are similarly unacceptable.  The paste form, although  acceptable for
 industrial  detergents,  is not favored for household  use.  Acceptable
 forms include the spray dried bead,  dry  blend  coarse powder, tablet,
 and liquid.   We did not undertake to produce the formulations in their
 final ready-to-package physical form. We did  determine, by drum drying,
 whether stable  solid non-hygroscopic, non-caking forms could be pro-
 duced.   We  also determined whether our formulations  could be made into
 stable  liquids  of adequately high concentrations.  No  attempts  were
 made to produce any of the formulations  in tablet  form,
An  experimental liquid formulation was not considered  satisfactory
unless  it contained only one liquid  phase and  was  sufficiently  con-
 centrated to  match currently successful  commercial liquids.  Solid
 formulations  were considered satisfactory only if  they were non-
caking,  non-hygroscopic  and free-flowing.  Aside from  these require-
ments relatively  little  emphasis  was placed on the physical form of
our  formulations.   Preferences  in physical form, appearance, fragrance,
etc. vary widely  from one detergent  manufacturer to  another.  They
are greatly influenced by considerations  of large  scale production

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and market Lag, and therefore we regarded the perfecting of physical
form as a secondary rather than a primary requirement of the project.
                                                   <

C.   SCOPE OF THE TESTING PROGRAM
                                                                    /
To be considered satisfactory the final formulations had to pass tests
in five different categories:  1) Algal stimulation; 2) Aquatic toxi-
city; 3) Biodegradability; 4) Hazard in use (human toxicity) and  5)
Laundering performance.  It is evident that such tests might be extend-
ed ad infinitum, and that the set of test protocols must be adopted on
a more or less arbitrary basis.  The tests specified in the contract
were judged at the time of their adoption to be optimum selection with-
in the budgetary and time limits of the project.  During the course of
the project they have changed relatively little, although some new tests
have been added.
Basic protocols for the tests in all five categories are given in Appen-
dix I.  The algal stimulation test procedures were adopted from the pro-
visional algal assay procedures ("PAAP") of the Pacific Northwest Water
Laboratory,  EPA, and were periodically revised to keep in conformity
with PAAP revisions.  The aquatic toxicity tests have remained unchanged
throughout the course of the program and require little comment.  It
should be noted that although the results of the snail and fish tests
are reported to two or three significant figures their reproducibility
is sometimes no better than two or three fold.  This is not uncommon
in bioassays where the number of specimens is limited.  The reprodu-
cibility of the diatom growth inhibition test is considerably better,
but it merits no more than a second significant figure.
In a program of this character the testing of biodegradability pre-
sents a difficult problem.  Even under the most favorable circumstances
it is difficult to determine the ease with which an organic compound
will be oxidatively consumed by microorganisms in a natural (stream)

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 or  artificial (sewage plant)  environment.  The usual procedure is to
 follow the disappearance  of the  test material by direct chemical anal-
 ysis.   This requires  an analytical method  that is reliable in the parts
 per million range.  Such  analytical methods were not available for the
 great  majority of surfactants and organic  builders of  interest in this
 program nor was it  feasible to develop  them.  Another  difficulty in
 testing for biodegradability is  that the distribution  of microorganism
 species in the inoculum or  "seed" that  is  used differs greatly from
 source to source.   A  third  major difficulty is that almost all seeds
 must undergo a period of  acclimation before they can attack an organic
 material that is new  to them,  even if that material proves ultimately
 to  be  biodegradable.   Contrariwise, by  careful acclimation microbes
 can be nurtured and developed to oxidatively consume almost any organic
 material,  even some that  are  considered germicides.  There is according-
 ly  much arbitrariness in  specifying an  acclimation procedure and a
 source of microbes.
 Except in those few cases where  analytical methods were available we
 used the biochemical  oxygen demand (BOD) to indicate aerobic biodegrad-
 ability,  comparing  it with  the chemical oxygen demand  (COD) and with
 the BOD of standard compounds  known to  be  readily biodegradable.  A
 variety of acclimation conditions and procedures were  used when neces-
 sary.   Similarly, a variety of different sludge sources were tried in
 cases  where  the first one tried  (EPA experimental sewage disposal unit
 in  the District of  Columbia)  failed to  initiate biodegradation.
 The  estimation of hazard  in use  is another area in which compromises
 and  arbitrary decisions must be  made in setting the procedure.  At the
 start  of the  program  five tests  were specified and written into the
 contract:  acute oral toxicity on rats, acute dermal toxicity on rab-
bits,  opthalmic  irritation  on  rabbits,  primary skin irritation on rab-
bits,  and primary skin irritation and sensitization on humans.
                                  8

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Food and Drug Administration protocols were used.   Relatively early in
the course of the project controversy over the possible teratogenic and
carcinogenic effects of NTA received much public attention.  At a some-
what later date similar' concern was expressed over possible esophageal
damage by excessively alkaline detergents.  It was decided not to per-
form any tests of carcinogenesis or teratogenesis  on candidate formula-
tions, but to include a test for esophageal damage.  The test adopted
was a provisional test, utilizing rabbits as the test animal, provided
by the Bureau of Product Safety, FDA.  Obviously,  materials such as NTA,
                  i
that have been objected to for properties we do not assess, were exclu-
ded from the program.
Tests with regard to laundering performance can be extended almost in-
definitely and can be the subject of much argument.  The test with which
we started and the rationale for adopting them were set forth in the
original proposal and incorporated into the contract.  They are outlined
in Section I of Appendix B.  The major points guiding their adoption
were:  1) that true soil removal and soil redeposition should be the
parameters of interest rather than optical effects due to brighteners;
2) that foaming was of minor importance, except insofar as a too per-
sistent foam might indicate poor rinsability; 3) that effects on the
fabric, including ash build-up and the build-up of organic residues,
were important parameters of performance.  During the course of the
project a low level but continuing effort was devoted to checking,
extending and modifying the test methods with a view toward greater
accuracy (accuracy here means the extent to which the tests correspond
with results obtained in actual practice) and more general acceptabil-
ity.  It should be. pointed out that there are at present no standard
laboratory tests for rating on an absolute basis the soil removing
power of laundry detergents.  Each manufacturer of these products has
his own set of protocols, and the accuracy of any single simple test

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 procedure is  not easy to defend.   Our  methods  development work and its
 adoption in the overall program is presented in Appendix B.

 D.    PLANNED  TECHNICAL APPROACHES
 Keeping in mind the scope and the  limitations  outlined above it was
 planned to divide the experimental work into three main areas.  The
 first and most important area would be the  actual preparation and test-
 ing of new detergent formulations.  From the formulations would ulti-
 mately come the new formulation we were seeking.  The second area of
 investigation would involve  the chemical analysis and performance evalu-
 ation of existing commercial detergents that appeared to be of interest.
 A  large number of new detergents appeared in the market during the
 course of the project.   A knowledge of their composition and their
 laundering performance was obviously of utmost importance to the pro-
 ject.   The third area of experimental  work  was to be concerned with
 methods development.   As mentioned above there was perforce a consid-
 erable degree of arbitrariness in  the  initial  selection of test methods,
 We  realized from the  beginning that the methods would probably require
 modification  as  the experimental work  proceeded and that the methods
 most  likely to require  modification would be those relating to launder-
 ing performance.
 The examination  of existing  products and the development of more ef-
 fective and realistic  test methods required little advance planning.
 The formulating  and testing  program however had to be carefully plan-
 ned even though,  as in  all R and D work,  these plans would have to be
 continuously modified and  reoriented on the basis of incoming results.
We can  consider the plan in  two separate parts, a formulations part
and a testing part.
                                  10

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Detergent formulations can be grouped into three large classes.   First,
those that are based on straight surfactant;  second,  those that  are,'
based on surfactant plus a precipitating builder;  and third,  those
based on a surfactant plus a non-precipitating or  chelating builder.
                                                              , I
This third class is represented by the conventional tripolyphosphate
built detergent.  In all three of these classes, it is understood that
the formulation can and usually does contain a certain amount of sili-
cate as an anti-corrosive agent.  This usually constitutes 5 to  10% of
the total mixture.  It also contains in the range  of .5 to 1.5%  sodium
carboxymethyl cellulose as an anti-redeposition agent and 'may contain
similarly small amounts of other anti-redeposition agents that are sup-
posedly more effective on the non-cellulosic man-made fibers. The
formulation may also contain fillers and standardizing materials,
usually sodium sulfate, as well as minor amounts of brightener,  perfume,
color and other adjuvants.  We shall consider in this discussion only -
                                                 *            '
the surfactant and the builder, assuming that the other ingredients will
be present as required in the final formulation.
It is generally recognized that straight synthetic surfactants,  unlike
soap, are poor in cotton washing.  Historically this is the reason.that
the market for synthetic surfactants remained quite limited until the
discovery of the specific building effect of the cbndensed phosphates.
It is also known,  however, that this inferior cotton washing property
varies considerably from surfactant to surfactant.  IAS, the most com-
monly used surfactant, is a mediocre cotton washer,.  Soap is notably
good.  We planned to explore systematically the cotton washing powers
of a range of surfactants, paying special attention to those claimed
to wash well in the absence of builders.  We refer to th,ese for  brevity
as "supersurfactants."  Testing would be limited of course to suRetr .
                                                           *    *  '  "
surfactants that appeared economically feasible.  It was also- planned" '
to test mixtures of soap with various lime soap dispersing surfactants.
                                  11 -

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 Such compositions have been widely mentioned from time to time as pos-
 sible substitutes for phosphate formulations in heavy duty laundering,
 and they have been used in bar toilet soaps for personal use.
 The theory of detergent action teaches broadly that the cleaning or
 deflocculating effect of the surfactant is opposed by the presence of
 polyvalent metallic cations in the solution, calcium ion being the com-
 monest and most important offender.  Possibly the most important action
 of a builder (although by no means its only action) is to remove cal-
 cium ions from solution.  One of the ways in which the builder may do
 this is by precipitating the calcium as an insoluble compound.  The
 best known example of such an effect is the use of sodium carbonate as
 a builder, the sodium carbonate precipitating out calcium ion and there-
 by allowing the surfactant to do its work.  Despite the first order
 simplicity of this theory it is known that the building effect of sodium
 carbonate varies greatly from one surfactant to another.  Formulations
 based essentially on a non-ionic surfactant plus a very high proportion
 of sodium carbonate were introduced on a large scale not too long after
 experimental work on the project started.  Due to their high alkalinity
 these materials appeared to have certain drawbacks with regard to
 safety in use,  and were therefore not considered ideal answers to the
 problem of developing a phosphate free detergent.  At a ^ater date
 household detergents containing a lower proportion of carbonate, usu-
ally with an equivalent amount of silicate,  were introduced in the
 market.   At about the same time there appeared detergents containing
 little or no carbonate,  but a high proportion of. silicate, in the
 range of 20-25% .of a high silica-to-soda ratio material.  This mate-
 rial has building properties although it is  neither .strictly precipita-
 ting or  sequestering.   The carbonate and silicate built materials
 however,  be grouped together for purposes of discussion.
                                   12

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The non-precipitating or sequestering builders remove calcium ion
by chemical reaction without forming a precipitate.   The prototype
of such builders is of course sodium tripolyphosphate.  The main
thrust of the program involved finding and formulating new builders
of this type.
Relatively few non-precipitating builders had been extensively explored,
or if they had been the information was not publicly available.  The
big exception was NTA which had not only been quite thoroughly'explored,
but had been used on a limited commercial basis and was generally con-
sidered to be the logical successor to the condensed phosphates.  Be-
cause of certain limitations with regard to physical form and large
scale manufacture, however, it was stated at that time that NTA could
be used only as a partial replacement for phosphate rather than a com-
plete replacement.  A considerable number of other possible candidates
were known but virtually nothing was known of their actual effect in
practical formulations.  It was strongly suspected that the building
effect of these materials would vary depending upon the surfactant with
which they were combined, i.e., certain of these builders might be very
effective with some surfactants but ineffective with LAS (the commonest
and least expensive synthetic surfactant but one of the more difficult
to build).  It was planned to solicit such materials from chemical
companies that were willing to supply them and to test them with a
variety of surfactants.  It was also planned to synthesize builders of
this type which might appear to be particularly promising, provided
they could not be obtained from primary chemical manufacturers.  It
was not envisioned, however, that such synthesis would constitute a
major proportion of the program.  We did not consider that the  in-
vention of new builders was our primary mission, and intended  to re-
sort to it only when necessary.
                                  13

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It was planned to make up  the  formulations for launderability testing
without actually putting them  together, i.e., the ingredients in pro-
per proportions would be put into the wash liquor without pre-mixing.
A separate aspect of the program would be undertaken for those combina-
tions of ingredients that  performed well.  This would involve putting
together the  ingredients into  a final formulation which would have to
have the acceptable physical characteristics mentioned above.
It was realized that the testing program, involving five different types
of tests, could not be well planned in advance but would have to be or-
ganized on an ad hoc basis.  The reason for this was the discrepancy in
the times required to carry out each test.  A chronic aquatic toxicity
test, for example, may take as much as a year to complete whereas a
soil accumulation test takes only about three days.  In general, the
laundering evaluations were conducted first.  Biodegradation and algal
stimulation tests followed in  that order.  Materials that looked pro-
mising in these tests were then submitted for acute aquatic toxicity
tests.  Product safety tests and chronic aquatic toxicity tests, as
well as bundle tests for laundering effectiveness were only conducted
on formulations which were entirely satisfactory from all other points
of view.  These tests are  by far the most time consuming and expensive.
It was planned in the testing program to make full use of all the in-
formation that could be obtained either in the open literature or from
the suppliers of the candidate materials.  Checking the validity of
such previously available  information is considerably less time con-
suming than developing it  from scratch.
                                  14

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                             EXPERIMENTAL

The basic soil removing formulations being sought were visualized as
consisting either of surfactant alone or of surfactant plus a non-
phosphate builder.  The candidate materials entering the program
were accordingly either surfactants or builders.  Depending on the in-
formation available, these materials might be tested first for biode-
gradability or aquatic toxicity or they might be made up into a formu-
lation and given the preliminary tests for laundering effectiveness.
Throughout the program most of the major areas of investigation were
being worked on simultaneously.  Whenever a material or a formulation
failed definitely to meet any of the important requirements it was
dropped from further consideration.  For efficiency in the program
the simpler tests were usually conducted first, and the more time
consuming tests later on the successful candidates.

A.   FORMULATING AND WASH TESTING
A total of several hundred different formulations were made up and
wash tested during the course of the program.  For purposes of discus-
sion they can be grouped into eight classes, based on the type of
builder used, as follows:
     1.   Unbuilt surfactants.  It is well known that surfactants
differ from one another in their washing power.  They also differ in
their response to any given builder.  Candidate surfactants were
generally tested by themselves to see if they were unusually effective
                                  15

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and might be made  the  basis  of a  completely unbuilt formulation.  Soap
and mixtures of  soap with  lime soap dispersing agents  (which are them-
selves  surfactants) are  included  in the  cateogry of unbuilt surfactant
formulations.
     2.   Carbonate and/or silicate-built  formulations.  Carbonate was
a  standard builder for soaps and  also  for  synthetic surfactants before
the advent of  condensed  phosphates.  It  is a precipitant for calcium
ion rather than  a  sequestrant.  A relatively small proportion, usual-
ly 8%,  of a high ratio silicate  (2:1 to  3.22:1) was included in all
our formulations to serve  as a corrosion inhibitor.  This is common
practice in detergent  formulation.  Higher quantities  (up to 40%) have
been recommended as builders and  as adjuncts in combination with other
builders.  We  tried them in  both  ways.   Silicates having an SiCL to
Na20 molar ratio less  than 2:1 were not  used because their high alkali-
nity was considered too  great a hazard in  use.
     3.   NTA.   At the start of the project NTA was regarded as the can-
didate  builder most likely to prove satisfactory and be adopted by the
industry.  Its properties  were therefore checked.  No  work with NTA
was done after the controversy developed over its possible hazards.
     4.   An analog of NTA was submitted as a candidate builder early
in the program.  This  compound, code named SAND, contains an acid amido
group (-CONH2) in  place  of one of the carboxyl groups  of NTA.  This
was tested to a  limited  extent, but later  in the program was deempha-
sized in favor of  another  NTA analog described below.
     5.   The material code  named SHIM or  HEIDA is the di-sodium salt
of phydroxyethylimino-diacetic acid.  This material was tested very
extensively.   SHIM is  the  earlier code name.  HEIDA is the more recent
name coined by the supplier.  Both names are used in this discussion,
                                  16

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         i-j-
SHIM referring to earlier samples and HEIDA to more recent ones.
                   (-
There appears to be no significant differences between them.
         '  .3-
     6.   Formulations based on organic polymeric builders.  It was
known at the start of the program that certain water-soluble polycar-
boxylated polymeric materials, of both natural and synthetic origin,
were builders of the sequestering type.  A considerable number of these
were explored and several were later tested intensively.  They included
only compounds containing no elements other than C, H and 0.
     7.   Formulations based on monomeric sequestering agents contain-
ing only C, H and 0.  Citric acid (as sodium salt) and carboxymethyl
oxysuccinic acid (abbreviated CMOS) were the most extensively tested.
     8.   A system of washing with unbuilt surfactants including an ion
exchange resin in the bath'to sequester the hardness was explored in a
preliminary manner.
The initial procedure for estimating the laundering potential of a new
compound was as follows:
     If the compound was a surfactant it was made up into a formulation
containing 12 - 25% active surfactant, 8% sodium silicate, 1% sodium
carboxymethylc-ellulose (NaCMC), 0'- 50% (sometimes more) builder, and
enough sodium siilfate to bring the total to 100%.  The exact percent-
age 6f surfactant used depended on its chemical composition and on the
type of surfactant against which it was being compared.  The magnitude
of the cleaning effect without builder1 was often a useful index of the
value of the surfactant in combinations.  The selection of builder and
the percentage used varied,  depending on the surfactant and the infor-
mation being sought.  The two surfactants used most often as standards
of comparison were our standard IAS sample and a widely used fatty
                                  17

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alcohol ethoxylate coded 68-127.*  The IAS was usually used at the
20 to 25%  level  in its  formulations and the 68-127 at 12%.  New surfac-
tants being compared against them were used at corresponding levels.
     If the compound of interest was a builder it was in most instances
tested with at least three  surfactants, two of them being IAS and
68-127.  The third and  other surfactants would be those of specific in-
terest in  connection with the builder being tested.  The formulations
generally  contained 12% of  68-127 or 25% IAS or an appropriate percen-
tage of whatever other  surfactant was being used.  In practically all
instances  the formulations  contained 8% silicate and 1% NaCMC.  The
percentage of builder was most often 30%, but 20% or 50% was some-
times used.  In  the primary launderability tests 0.3% total formula-
tion was used in 200 ppm hard water.  If the calcium sequestering
power of the builder was known a high enough percentage (20% or 30%)
was used to take care of the hardness.  If the, calcium sequestering
power was  unknown, and/or was suspected of being low, 50% was used.
In the later stages of  the  program experimental builders were rou-
tinely tested for calcium sequestering power.  This was done by
titrating  with a standard solution of calcium chloride, using an
Orion Research,  Inc., Divalent Cation Electrode model 92-32 to mon-
itor the calcium ion concentration.  The genera.1 procedure was to
                            *%
start with 100 ml of 2 x 10*"  molar calcium chloride solution
(equivalent to 200 ppm hardness as CaCOo) and titrate into a 2%
solution of the  sequestrant.  Typical titration curves for strong v.
weak and high efficiency v. low efficiency sequestrants of interest
are shown  in Figures 46-49.
(*See Appendix C for description of coded materials.)
                                  18

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     The primary launderability test used throughout most of the pro-
gram is described in Appendix B.  Four cycles of soiling and washing
were usedj and four soil-fabric combinations:  dry vacuum cleaner
soil and .sebum soil, on cotton and a 50:50 cotton polyester blend
finished for durapress. (permanent press)..  Earlier straight polyester
(unfinished) was also used as a test fabric, and some 65 polyester:
35 cotton durapress finished fabric was also used.  The launder-
ability behavior of these fabrics was sufficiently close to that of
the 50:50 blend to justify dropping them, and devoting the time saved
to examining more detergents.  The AATCC #124 and AHAM detergents
were us-ed as standards, together with any other comparison deter-
gents that were considered appropriate to the specific test.  The
reflectance readings were automatically transferred to punched tape
which was fed to a computer.  The computer was programmed to print
out not only absolute reflectance readings but also the differences
in reflectance between the test detergent washed swatches and the
standard detergent washed swatches.  These differences, or "delta
values", greatly facilitate comparison.  Their significance can be
judged on the basis of their statistical confidence limits, also
printed out by the computer but not included in the tables of this
report.  In most of the runs shown in the tables delta values less
than one unit do not indicate a difference that would be signifi-
cant in practice.  Modifications of this primary multicycle test are
detailed in Appendix B.  Table headings indicate which of the tests
was, used to obtain the data in the tables.
     Aside from the primary multicycle tests three other tests for
launderability were used.  These tests were applied mainly to the
more promising formulations.  They were:  single cycle detergency
v. concentration tests using purchased cotton soil cloth (Empa);
single cycle detergency v.  concentration tests on cotton and blend
                                19

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 soil cloths prepared in this laboratory ("Colgate" soil);  and  the
 bundle test (ASTM D-2960-7IT).   These are described in Appendix  B.
 Data from the single cycle tests are shown in the Figures  as plots
 of soil removal v. detergent concentration.  Some of the multi-
 cycle tests were extended to include a range of detergent  concentra-
 tions less than the 0.3% used in screening.  Data from these tests
 are also presented in graphic form.   Data from the bundle  tests  are
 included in the text of the sections headed RESULTS and DISCUSSION
 respectively.  In many instances launderability tests were performed
 at water hardnesses other than 200 ppm.  This is indicated in  table
 and graph headings and in the Text.
      In all tests for launderability,  including single cycle,  multi-
 cycle,  and bundle tests (except where specifically noted),  rede-
 position swatches were included and  measured.  The data accumulated
 on redeposition is therefore fully as  voluminous as the data on
 soil removal.  It did not at any point, however,  present any ano-
 malies  nor did it differ from what might have been expected on the
 basis of the soil removal results.   It is therefore omitted from this
 report  on the basis that any added significance it might contribute
 would not justify the excessive space  required.

 B.    PHYSICAL FORM
 Experimental work directed toward producing formulations of commer-
 cially  acceptable physical form was  necessarily limited.   The  abil-
 ity to  produce a beaded solid form of  detergent on a large scale
 cannot  be guaranteed by laboratory scale experimentation.   We  had
 available, however,  a laboratory size  drum drier  (sometimes referred
 to  as a roller drier),  and the  behavior of materials  in this equip-
ment  can usually be  extrapolated with  confidence.   In particular,
                               20

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drum drying on a laboratory scale can indicate very well whether the
formulation will be hygroscopic, or have a tendency to sinter or
become compacted, or have other unacceptable faults.  Liquid formu-
lations that are satisfactory when made on a laboratory scale usually
present no difficulty in large scale operation.
The only formulations that we tried to put together in assembled
form (solid if possible; liquid if a satisfactory solid form could
not readily be made on the drum drier or by dry mixing) were those
that appeared most promising in the primary launderability tests and
had not been rejected in any of the other tests.  These included
SAND and SHIM formulations, silicate-citrate formulations and NTA
formulations.  The NTA formulations were developed during a period
when eventual NTA acceptance (frpm the hazard-in-use point of view)
was considered highly probable.  In preparing the dry formulations
the ingredients were dissolved or slurried in a sufficient amount
of water to enable easy transfer to the hot drums, and were thor-
oughly mixed while transferring to assure homogeneity.  No lengthy
hot crutching, common in large scale spray drying operations, was
used; and the possible effects of such treatment were not determined.

C.   EFFECT ON FABRIC
Detergents that contained large proportions of soap and/or of car-
bonate, and that had proved promising in preliminary tests were
tested for effect on fabric as follows:  Swatches of the fabric
were put through a series of 20 to 50 washing-drying cycles with no
intermediate soiling.  They were then analyzed for ash content and
for alcohol extractable content in the usual manner.
                               21

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D.   AQUATIC  TOXICITY
Two  types  of  aquatic  toxicity test were included in the program:
an acute test and  a chronic  or  long term test.  Both are described
in Appendix A.  All aquatic  toxicity testing was done by the Depart-
ment of Limnology, Academy of Natural Sciences, Philadelphia.  The
acute  test was  applied  only  to  compositions that showed promise of
good performance.  Together  with biodegradability and algal stimu-
lation the acute aquatic toxicity test constituted the second level
of testing to which candidate compositions were submitted.
The  chronic toxicity  test consists of an extensive series performed
over a protracted  period on  a relatively large number of species.
Only two compositions over the  whole duration of the program were
put  through the chronic test protocols.  These were the citrate-
silicate-ether  carboxylate composition identified as 64-1, and the
control detergent AATCCWOB.  It was considered necessary to test the
latter compound because no literature exists on the aquatic toxicity
of well identified, typical, phosphate-containing, heavy duty house-
hold laundering detergents.  The AATCCWOB detergent qualifies on
all  counts and  can therefore provide a benchmark against which can-
didate formulations can reasonably be judged.  Although the deter-
gent with  brightener would have been more realistic the brightener-
free material was better suited as a standard of comparison for the
brightener-free candidate experimental detergents.

E.   BIODEGRADABILITY AND ALGAL STIMULATION
Tests  for biodegradability and stimulation of algal growth, like the
acute aquatic toxicity tests, were applied only to candidates that
showed promise of good  laundering performance.  The protocols for
these tests are described in Appendix A.
                               22

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F.   HAZARD IN USE
Testing for hazard in use, as outlined in Appendix A,  is lengthy and
extensive.  Very few of the materials and compositions used in the
program were submitted to these procedures.  Materials known to be
hazardous were excluded from the program.  Suppliers were requested
to submit all data on hazard which they had, and, in the case of
materials which looked especially promising from other standpoints,
to develop as much valid acceptable data on hazard as was possible.

G.   WASHING WITH ION EXCHANGE RESINS
The concept of using a suitable packet of cation exchange resin in the
washing machine, to serve as a substitute for the phosphate builder
component of the detergent, was first considered by the group working
on this project about April 1971.  Experimental work to demonstrate
its feasibility was performed during the following two months and was
reported in Monthly Reports Nos. 12 and 13 of this series dated
June 10, 1971 and July 10, 1971 respectively.  This work was not men-
tioned in the Interim Report dated January 7, 1972.  It is included
herein for purposes of record, and to serve as a basis for future
work that might be undertaken along these lines.
It is well known that many surfactants, including some of the inex-
pensive ones commonly used in detergent compositions, give good wash-
ing performance at low concentrations in the absence of builder
                                 I [
provided the concentration of Ca   or other polyvalent metallic cations
in the system is very low.  It would seem, on this basis, that an
efficient convenient water softener system would enable the house-
holder to do her laundry with surfactant alone.  The catch in this
proposition is that the concentration of Ca-H- must be very low,
preferably less than 10"  molar  (0.1 ppm as CaCO-) for LAS, and
                               23

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not more  than  about  5 ppm for  the more effective surfactants.  The
amount  of Ca++ introduced by the soiled fabric is often sufficient to
exceed  this  limit  even  after it has become completely diffused into
and diluted  by the wash water.  Until such time as it has become dif-
fused,  the concentration  at  the fiber surface where detergent action
is occurring far exceeds  this  limit.  We therefore must soften the
wash water in  the  machine as the washing is taking place.  There are
at least  two ways  to do this.  One would be to have an ion exchange
unit mounted on the  washing  machine together with a pump to circulate
the wash  liquor through the  unit.  A simpler way, and one which could
be used with existing washing machines, would be to put a cloth bag
(or other sturdy porous container) of ion exchange resin beads into
the wash  liquor with the  laundry load.  Calculations indicate that
the amount of  resin  necessary  to soften the incoming water and take
care of calcium ion  from  the fabric load would not be excessive,
and the cannister  or bag  of  resin should remain effective through
several launderings.  When spent (or after a stipulated number of
uses) it  could  be  regenerated with brine by the householder or turned
in for  regeneration  in  exchange for a fresh bag.  To explore the
feasibility  of  this  idea  EMPA cotton soil cloth, which behaves quali-
tatively  (although not  quantitatively) like cotton in soil accumu-
lation  tests, was washed  in  200 ppm hard water with an unbuilt IAS
formulation,  with  and without ion exchange resin present in the
wash bath.  The resin beads  were contained in a sturdy cotton bag,
which was stirred  around  in  the wash liquor as part of the fabric
load.   The load of resin  in  each bag was 5 grams, corresponding
to about  11 oz. in an ordinary 17 gallon  washing machine.  This is
theoretically adequate  to  soften several batches of 200 ppm wash
liquor before requiring regeneration.  For purposes of comparison
similar washings were performed using the unbuilt formulations in
                                24

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distilled water and using phosphate-built formulations in hard water,
both in the absence of resin.  The unbuilt formulations were also
used in hard water in the absence of resin,  and gave the expected
poor soil removal.  Two cation exchange resins were used, both in
the sodium form:   Dowex 50 W-X8,  a sulfonic  acid type; and Amber-
lite IRC-50, a carboxylic type.
                              25

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                               RESULTS

 The experimental data  involve  seven categories of properties:  laun-
 derability, physical form, effect on fabric, aquatic toxicity, biode-
 gradability, algal stimulation and hazard in use.  They also involve
 eight different categories of  compositions:  unbuilt surfactants,
 carbonate/silicate, NTA, SAND, SHIM-HEIDA, polymeric builders, mono-
 neric builders and ion exchange resins.  It is obvious that not all
 compositions, nor even a representative of every category of composi-
 tion, were examined with regard to all property categories.  Some com-
 positions were studied much more extensively than others and, due to
 changing priorities during the course of the program, it was not always
 the most promising compositions that received most attention.  Among
 the property categories launderability provided the most data.  For
 purposes of presentation the processed data are therefore organized
 from two different standpoints.  Data on all of the properties except
 launderability (also referred  to as washing power or soil removing
 power) are presented in single tables which show the results for in-
dividual compositions of several different categories.  In the laun-
derability category the data are partly tabulated, partly graphed
and partly (bundle test data)  presented in the text.  By no means all
of the formulations that were examined are reported in the tables.
Omitted are those which failed badly in one respect or another at an
early stage.   Also omitted are those poorly characterized or otherwise
failing to meet the requirements discussed earlier in this report.
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Results of the screening program on launderability are presented in
Tables 1-7.  These tables are the product of considerable processing,
abridgement and condensation of raw data obtained over a period of
three years.  The changes in washing procedure details that occurred
during this period are explained fully in Appendix B, and each pro-
cedure is described.  For convenience in following the presentation,
                   b
however, the following explicit notes on column headings in the tables
are given.  Tables 1, 2, 3, 3a, 4, 5, 6, and 7 refer to the multi-
cycle or soil accumulation washing procedures outlined in Appendix B
as "procedures 4 and 5" or as the "dry soil" and "oily soil" procedures
In the column headings of these tables "vacuum soil" is synonymous
with "dry" or "procedure 4" soil.  "Sebum soil" is synonymous with
"oily" or "procedure 5" soil.  The "blend fabric" referred to is a
50:50 cotton-polyester sheeting finished for permanent press.  It is
also referred to at places in this report as "durapress" fabric.
These tables show only the "delta 6" values against the AATCC standard
detergent after four cycles of soiling and washing.  These values are
the difference in reflectance between the fabrics washed in standard
detergent and those washed in test detergent, as measured on the re-
flactometer with the green filter in place.  As shown in Appendix B,
measurements were also made with the yellow and blue Bx filters and
confidence limits and whiteness values were computed.  Redeposition
swatches were also included in the wash load.  Their reflectances
were measured and the data processed in the same way.  The redepos-
ition results have been omitted  for  the  sake  of brevity.   There is
of course a much smaller range of reflectance and whiteness values
among the redeposition swatches than among the soiled swatches, and  in
ranking the formulations for overall laundering performance soil re-
moval performance greatly outweighs redeposition performance.   In
practically all instances the redeposition behavior paralleled  the
                                27

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 soil  removal behavior closely enough to have negligible  effect  on the
 ranking.  Also omitted are delta 6 (and "delta BX") values  against the
 AHAM  standard detergent which was used in almost  all  the important runs,
 and against various  commercial detergents (notably Tide  XK  and  Sears
 non-phosphate detergent) which were  used in a considerable  proportion
 of the  runs.  In a large number of the earlier runs 100% polyester
 swatches  were included with cotton and/or blend fabric.   These  data
 have  also been omitted.
 The delta G values in the tables represent the number of reflectance
 units difference between the standard-washed swatches and the test-
 washed  swatches.  A positive value means the standard-washed swatches
 were  brighter;  a negative value means the test-washed swatches  were
 brighter.   Values in different series are not directly comparable, be-
 cause the intensity  of soiling necessarily varies  from series to series,
 although  with care it can be held reasonably constant.   Strong  soiling
 generally leads to larger delta G values whether  positive or negative.
 The "Proportions" column gives the percentage composition of the for-
 mulation.   The  first number in line  represents percentage of surfac-
 tant; the second number percentage of silicate.  When no letters follow
 the silicate number  it  means that silicate G (Philadelphia  Quartz Co.)
was used.   Letters indicate other types  of silicate (all in this re-
port  from this  same  supplier).   The  third number  is NaCMC,  in all but
a very  few  instances  used at the one percent level.   The fourth number
 is percent  builder;  and the last number  percent sodium sulfate  unless
otherwise designated.   If the surfactant  is  a mixture (as in items 16 -
 18 in Table  2)  the first two numbers  give the percentage of each sur-
factant .
Tables  la,  6a and 7a  relate  to  "Spangler  soil"  ("procedure  3")  three
cycle soil accumulation runs, and  show the "delta W"  (delta whiteness)
                                   28

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values on blend and cotton fabrics.  Tables 7b and 7c give whiteness
values and show results for all five washing procedures described in
Appendix B.  The calculation of "whiteness" from the primary reflectance
readings is also shown in Appendix B.
Studies of washing power (launderability or soil removal) of the various
compositions tested as a function of detergent concentration are re-
ported in graphic form in figures 1-36.  Most of these studies were
made with the Colgate soil, also referred to as "procedure 2" in Appen-
dix B.  Some were made with Empa cotton ("procedure 1") and some by
the Spangler soil multicycle procedure ("procedure 3").  The procedure
in each case is shown in the legend.
Data on physical form are shown in Tables 8 and 8a.  All of these were
developed during the first half of the program.  As the program de-
veloped it was realized that commercially satisfactory forms might be
capable of development in large scale equipment by experienced manu-
facturing organizations, even though they could not be made in our
limited laboratory facilities.  Emphasis was therefore placed on those
other properties of the formulation that could be more realistically
assessed.
Work performed with respect to effect of the formulations on the sub-
strate fabric was also limited and is summarized in Table 13.
Acute aquatic toxicity data are summarized in Table 10.  The complete
reports on the two chronic aquatic toxicity tests that were performed,
one on Formulation 64-1, the other oil the control high-phosphate de-
tergent AATCCWOB, are presented separately as Appendix E.
Estimates of biodegradability are presented in Table 11.  As explained
in Appendix A these estimates are based on BOD and COD tests and
therefore relate only to aerobic biodegradation.  A definitive study

                                   29

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of the biodegradability of  any  single compound is in itself an ex-
tensive  project,  and  even a complete study of BOD (varying temperatures,
acclimation conditions,  duration of test, etc.)  is  lengthy.  The data
obtained in this  program, although quantitative  and extensive, are
considered  too  limited  in scope to merit tabulation.  The compounds
and  formulations  are  therefore  grouped  into three classes:  those
readily  biodegraded in  the  test and therefore judged almost certain
to biodegrade satisfactorily in natural waters and  in secondary sewage
treatment;  those  sufficiently resistant in the test to be judged un-
likely to biodegrade  in a reasonable time under  the above conditions;
those of intermediate resistance, on which extended studies should be
made before judging their acceptability.
Data on  algal stimulation are summarized in Table 9.
Data on  hazard  in use are summarized in Table 12.
All of the  above  tables  and diagrams will be referred to in the pre-
sentation of results  immediately following.  The presentation is
arranged according to composition categories.

A.   UNBUILT SURFACTANTS
Referring to Table 1  it  appears that relatively  few straight surfac-
tants, or surfactants built only with silicate,  have a chance of
washing  satisfactorily at practical concentration levels.
The anionic  sulfonates,  particularly LAS, showed relatively little
washing  power in  the  unbuilt  state (Items 60 through 66) even when used
at the 25%  level  in the  formulation.  The same was true for the alpha
olefin sulfonates (Items  31 through 35) and the  ether sulfates (Items
36 through 42) although  these were not  tested at a  level higher than
20%.   The fatty alcohol  ethoxylates, the most extensively tested
                                   30

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surfactants (Items 19 through 21), showed increasing effectiveness
on sebum soil with increasing concentration,  but they still did not
appear effective enough for practical consideration.  One of the
hydroxylated nonionics, Code 43-83, and the commercial detergent ex-
tract 32-237 did a creditable job at the 25% level particularly when
built with excess silicate (Items 26 and 58).  Possibly the most power-
ful non-soap surfactants in the unbuilt state were the sulfo zwit-
terionic materials (Items 52 and 55).  Even these did not appear strong
enough to be considered practical competitors for phosphate detergents.
The one material that appeared to wash as well as the reference phos-
phate-built detergent was soap.  Item 69 indicates that a formulation
consisting essentially of 85% low titer soap and 15% of a high ratio
silicate washed about as well as the standard phosphate detergent.
It must be borne in mind, of course, that both formulations are being
tested at the same concentration, namely .3%, and that the standard
phosphate detergent contains only about 20% active surfactant whereas
this soap formulation contains 85% active surfactant.  Item #70,
which contains in addition to soap a substantial proportion of a
lime-dispersing anionic surfactant, performed even better than the
straight soap.
Continuing in Table la, IAS (items 81-84) and fatty alcohol ethoxylate
(items 74-76) still appear significantly poorer than the control deter-
gent even at the relatively high concentration of 27%.  The mixture
of fatty alcohol ethoxylate (FAEN) and fatty diethanolamide (items 79-
80) appears better than the FAEN alone, giving another indication that
mixtures of surfactants might be better than single species.  The
first such indication was the performance of the commercial detergent
extract 32-237 (items 57-59 in Table 1).  Surfactant 90-730 was stated
by the supplier to be intended for use without phosphate, but in
this test it proved distinctly inferior to the control detergent and
                                   31

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 about  equal  to  unbuilt  IAS.   The  soap-lime  soap dispenser  (LSD)combina-
 tions  (items 85-87)  again showed  superior launderability.
 Detergency vs.  concentration studies were performed on  the more prom-
 ising  of  these  materials.  Figures  1-4  show the results of tests on
 soap and  soap-LSD combinations  on Empa  cotton soil cloth.  In the
 200 ppm water of this test all  the  soap-based compositions (at approx-
 imately 85%  surfactant) were inferior  to the control detergent (approx-
 imately 20%  surfactant) up to .2% concentration.  Above .2% the soap
 compositions performed  better than  the  control detergent in this test.
 The sulfonate zwitterionics1  behavior  on Colgate  soil is shown in
 Figures 13-14.   These materials performed remarkably well in a 30%
 ative  composition, being  especially effective in  the concentration
 range  under  .15% and especially under  .1%.   These zwitterionics are
 not identical to those  of  Table 1,  but  they behave in a similar manner.
 The behavior of two  lime  soap dispersing agents (used in the soap LSD
 compositions and purported to have  good detersive properties when used
 alone)  is  shown in Figures 15-16.   They did not fulfill expectations.
 Surfactant 90-730 was tested extensively, not only against the control
 detergent AATCCWOB (Figures  5-6)  but also against IAS in a comparable
 formulation  (Figures 7-10) and against  one  of the more promising
 non-phosphate built  compositions  (Figures 11-12).  On both Spangler
 and Colgate  soils it exhibits the same  behavior.  It is superior
 to AATCCWOB  at  concentrations under .15% (in this 200 ppm water) bat
 significantly less effective  at higher  concentrations.  It is super-
 ior to LAS at all concentrations  under  .3%.   Like most other non-
phosphate compositions the 90-730 formulation looks comparatively
better on cotton than on blend fabric.
                                   32

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Following up on the idea that mixtures of surfactants might be more
effective than the single components two commercial liquid non-
phosphate detergents consisting essentially of surfactants without
builder were tested.  Results are shown in Figures 17-20.  These pro-
ducts, both of which contain in the neighborhood of 40% surfactant
and include both anionic and nonionic surfactants, behaved remarkably
alike.  In the low concentration ranges, below .1 to .15%, they are
superior to AATCCWOB.  Above about .15% they are not quite equal to
AATCCWOB, although on cotton fabric they are almost equal.
The only unbuilt surfactant that was bundle tested was the 90-730
formulation containing 27% active surfactant.  This was tested
against AATCCWOB at .15% in Rockville tap water.  Both the panel
ratings and the reflectometer readings showed the AATCCWOB signifi-
cantly superior at the end of 6 cycles.  At this low concentration,
however, even the AATCCWOB did not get the laundry satisfactorily
clean, and the test cannot therefore be considered satisfactory.  No
further launderability work, however, was done with the 90-730 sur-
factant.  The sample at hand had caused more yellowing than the control
in all the tests.  Properties other than launderability are shown
in the appropriate tables.
The soap and soap-LSD formulations were examined for effect on the
fabric.  Data in Table 13 show that the ash content increases con-
siderably more and the alcohol extractable content much more with
these detergents than with AATCCWOB.  The LSD helps to keep the ash
content down to a reasonable level, but has less effect on the al-
cohol extractable content.
                                  33

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 B.    FORMULATIONS  BUILT WITH CARBONATE AND/OR  SILICATE
 Early in the  course  of the  project  interest  in carbonate as a builder
 was very high.  This was  largely  a  result  of the introduction into
 the retail market  by Sears  Roebuck  of a detergent containing approxi-
 mately 10% of a fatty alcohol ethoxylate surfactant and 65% sodium
 carbonate.  A relatively  small number of high  carbonate formulations
 were  accordingly prepared and examined for launderability with re-
 sults shown in Table 6.   These data indicate that certain nonionic
 surfactants and some surfactant mixtures provide reasonably good
 laundering performance in high carbonate formulations, provided a
 sufficient percentage of  surfactant is present.  Later in the program
 two commercial detergents,  one containing  about 20% carbonate and the
 other free of carbonate but containing about 20% of silicate, were
 tested using  Colgate soil.   The results are  shown in Figures 21-22.
 The fact  that detergents  of high  carbonate content cause extensive
 ash build-up  in the  substrate fabric is evidenced in Table 13.
 Data  in Tables 1,  la, 7 and 7a show that a high silicate content
 tends  to  improve launderability significantly,  and the effect on the
 fabric  (Table 13)  is not  too objectionable.
High  carbonate apparently has  no  unfavorable effect on algal growth
 (item 8,  Table 9), nor on acute aquatic toxicity (item 10, Table 10).
It may  pose a possible hazard  problem with regard to esophageal ir-
ritation  (Table 12).

C.   FORMULATIONS BUILT WITH NTA  (nitrilotriacetic acid)
In the  early  stages  of the  program,  and within the soap and deter-
gent industry even before regulatory action  on phosphate was being
considered,  NTA was  regarded as the most promising phosphate
                                   34

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replacement.  Accordingly a modicum of launderability testing was
done to check the efficacy of this compound.
Table 3 shows that NTA is a powerful builder for all the classes of
surfactant which were tested.  It is particularly effective with the
alpha olefin sulfonates (Items 3 and 7) giving negative delta G
values on all four fabric-soil combinations.  One of the big ques-
tions with regard to NTA, aside from the question of its possible
hazard in use, was whether it could be made into a detergent of ac-
ceptable physical form.  It was found, as shown in Table 8, that the
combination of NTA with alpha olefin sulfonate formed a dry powder
of good physical characteristics.
This formulation (Item 7 of Table 3) was examined for laundering per-
formance over a range of water hardnesses and at concentrations rang-
ing from .1 to .3%.  The results are shown in Table 3-A.  It is
evident that this formulation is a rasonably good match for the stan-
dard phosphate detergent over the whole range of use conditions.
It is significantly inferior only on sebum soiled blend fabric at
low concentrations in hard water.  When enough detergent is used to
soften the water the performance again matches that of the phosphate
standard.  In this connection it should be borne in mind that this
formulation contains 30% NTA as against 40% tripolyphosphate in
the standard detergent.
Acute aquatic toxicity tests on NTA showed it to have no adverse
effects on the test organisms even at 500 ppm (Table 10, item 23).
BOD tests (data not shown) indicated that NTA is not as rapidly
biodegraded as LAS or some of the other proposed phosphate replace-
ments such as citrate.
                                  35

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 D.    SAND FORMUIATIONS
 SAND is the abbreviation for the disodium salt  of the monoamido
 derivative of nitrilotriacetic acid.   This material was  offered  for
 testing relatively early in the program.   The supplier,  on  the basis
 of  his own laboratory work was convinced  that this material strongly
 resisted hydrolysis and therefore could not be  considered simply as
 a reservoir or source for NTA.  On this basis the compound  was tested
 for launderability and other properties.   Launderability data on
 the more important SAND formulations  are  shown  in Table  4.   SAND,
 like NTA,  is a good builder for all types of surfactants but appears
 less effective on LAS and on the alkane sulfonate type of surfactant
 than might be desired.   It is exceptionally effective with  some  of
 the ether  carboxylate surfactants (Item 6)  and  also with the fatty
 alcohol ethoxylates.
 Table 8 shows that SAND is a very desirable constitutent of dry  mixes,
 being one  of the  very few materials that  appears  to form a  satisfac-
 tory dry mix with the fatty alcohol ethoxylates as well  as  with  other
 surfactants  that  are  normally easier  to dry.
As  shown in  Table 10,  item 25,  SAND has no  significant effect on the
 test  organisms  used in the aquatic toxicity tests.  Biodegradability
 tests  (data  not shown)  indicated about  the  same degree of resis-
 tance  to aerobic  biodegradation as shown  by NTA.

E.    SHIM  (HEIDA)  FORMUIATIONS
SHIM,  later  abbreviated HEIDA by the  supplier, was submitted for study
early  in the  program.   It  is  the disodium salt of beta hydroxyethyl
iminodiacetic acid.
                                  36

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Referring to Table 5, SHIM,  like SAND,  is a good builder for all types
of surfactants although it is less effective on IAS than on the others.
Comparing Items 1 and 2 it appears that 30% SHIM in a formulation
is sufficient when the formulation is used at the .3% level in 200 ppm
water.  In our essentially limited! work on physical forms we found
that SHIM compositions failed to give good drum dried products.  It
did prove possible, however,  as shown in Table 8-A, to make stable
liquid formulations containing SHIM as a builder.  A hydrotrope was
necessary, sodium octenyl succinate being best for the nonionic,
and sodium xylene sulfonate being best for the anionics.  The essen-
tial antiredeposition agent NaCMC would not dissolve in any of these
compositions, but it can presumably be suspended satisfactorily as
it is in present day commercial heavy duty liquids.
When used as a builder for LAS at the 30% level SHIM showed excellent
performance in the Colgate soil test (Figures 23-24).  At a concen-
tration level of .2% or higher, where sufficient SHIM is present to
overcome all the water hardness, the absolute level of soil removal
is equal to that of the control high-phosphate detergent, even on
blend fabric.
Two different SHIM formulations were bundle tested.  The first was a
20/8/1/30/41 formulation in which the surfactant was alpha olefin sul-
fonate code 22-155.  This was tested at 0.2% concentration in Rockville
tap water against the AHAM detergent (cf. Appendix B) .  At the end of
six cycles the panel rated AHAM superior by a score of 9.75 to 6.25.
This difference was  later shown to be due to a larger residue of the
original mill-finish fluorescent whitening agent in the AHAM washed
fabrics, than in the  SHIM washed fabrics.  The former appeared slightly
whiter to the eye  in daylight even though the soil content,was not
lower.  Instrumental readings on the pillowslips of both blend  and
cotton fabrics showed no  significant difference between the test  and
the control  formulations.  The  second bundle test was performed on
                                  37

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 a 20/8/1/30/41 formulation in which the surfactant was  IAS.   This
 was tested at 0.3% in tap water against AATCCWOB.   In this test
 the panel gave the SHIM formulation the non-significant numerical
 edge 9.65 to 9.35.  Instrumental measurements of reflectance  were
 made on all the laundered items (not only on the pillowslips).   Sta-
 tistical analysis as well as eyeball judgment of the data showed no
 significant difference between the two detergents.  At  this ample  con-
 centration both bundles of laundry were satisfactorily  clean  from
 the consumers' point of view.
 SHIM proved to be fully satisfactory with regard to biodegradability
 (Table 11) acute aquatic toxicity (Table 10)  and algal  stimulation
 (Table 9).  Hazard tests were run on a 25% aqueous solution of the
 unformulated material (item 56-445 in Table 12)  and on  two finished
 formulations 65-1 and 65-2 containing respectively 18%  and 25% of
 100% active SHIM.  The results (Table 12) suggest  that  SHIM is close
 to the borderline with regard to both oral and dermal toxicity,  and
 that the toxicity of a composition containing SHIM may  depend to a
 great extent on the character of the accompanying  surfactant.  It
 should be noted that these data are quite limited,  and  that much more
 extensive testing is needed before judging the degree of hazard  which
 SHIM presents.

 F.    FORMULATIONS BASED ON POLYMERIC BUILDERS
 The  launderability data in Table 6 which were developed early in the
 program show that the polymeric builders vary quite widely in their
 effect,  and  even those which are effective with  one type of surfac-
 tant  may be  quite unsatisfactory with another.   Several of the
materials in this  table,  notably the builder  coded 40-310, are de-
 scribed  in the  patent literature as  being quite  effective.  It is
unfortunately quite  resistant  to biodegradation  under ordinary
                                   38

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circumstances.  None of the materials shown in this table has been
satisfactorily biodegradable.  There are of course many polymers,  such
as the proteins and some of the carbohydrates, that are readily bio-
degradable, and there is no reason why a combination that exhibits good
biodegradability together with good building power should not exist.
A continuing effort was made throughout the course of the project  to
discover polymeric builders that were biodegradable.  Preliminary
launderability tests (made prior to or simultaneously with biode-
gradability tests) are shown in Table 6a.  The polyacrylic acid
builders were studied more extensively than any other class for the
following reasons:  first, they had a more favorable economic picture
than most of the other materials; second, they were available in a
wide range of molecular weights; third, they were known to be toxi-
cologically harmless and non-stimulating to the growth of algae.
The philosophy was that monomeric acrylic acid is biodegradable but
not a builder; acrylic polymer of high molecular weight is a good
builder but is not biodegradable.  Somewhere in between we must come
to a molecular weight range where the material has both biodegrad-
ability and building power or has neither.  The series of acrylic
polymers 92-745, 100-823 and 100-824 graded in average molecular
weight from about 3000 to well under 1000 were studied on this basis.
The chelation curves in Figure 49 show that the lower molecular weight
material has considerably lowered sequestering power, but still
might have a satisfactory building effect.  Figures 25 and 26 show
the detersive effect of Calnox 214 DN a polyacrylic acid with a
stated mean molecular weight of 750.  It performed remarkably well
on cotton on this test, and even on blend fabric it was fully satis-
factory in the IAS formulation, at 0.3% concentration.  This material
has low aquatic toxicity.  It is at least partially biodegradable,
although the action is slow.
                                   39

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 A polymeric builder that has  been extensively explored and reported
 upon by the producer is  the hydroxylated  acrylic  identified as
 POCNa (code 104-860).  The sequestration  curve on this material
 (Figure 48) indicates  that a  high proportion would have to be used
 in a detergent  formulation to produce  a satisfactory building effect.
 Figures 27-28 show that  in an IAS formulation at  50% active content
 it performed well in the concentration range about 0.2%, especially
 on blend fabric.   This material was made  up  with  IAS to a 20/8/1/50/21
 formulation,  and  was bundle tested against AATCCWOB at 0.3% in tap
 water.   After 6 cycles both bundles were  satisfactorily clean.  The
 panel rated the control  detergent 10.9 against 9.1 for the POCNa for-
 mulation,  an insignificant difference.  Instrumental reflectance read-
 ings were  made  on all  laundered items.  They showed no significant
 difference between the two detergents.  The  biodegradation was faster
 and more extensive than  that  of any other polymeric builder tested
 (Table  11).   The  aquatic toxicity, like that of all other polymers
 tested,  was  low.
 Homopolymers  and  copolymers of maleic  acid have long been known to
 have remarkably good building powers,  but to be quite resistant to
 biodegradation.  A recent patent  application (Netherlands Applica-
 tion 7205685  to Shell  International Research)  describes certain low
 molecular weight  telomers  of  maleic acid  which are stated to be bio-
 degradable.  A  telomer of this type was prepared, following the patent
 example  closely, using isopropyl  acetate  as  the telogen.  The product
was  purifed thoroughly and characterized  by  the usual tests, and
 given the code  designation 106-866.  The  chelation curve (Figure 46)
 showed  it to be an exceptionally  powerful and  efficient sequestrant.
Detergency data are  shown in  Table 6a, items  37-40, and in Figures 29-
32.  When used  in  equal quantities it  appears  fully equal to sodium
tripolyphbsphate as a  builder  for LAS  in  these testing regimens.
                                   40

-------
Due to termination of the program this material was not bundle tested,
It performed well in the aquatic toxicity test.  In the BOD test it
showed moderately extensive and rapid oxygen absorption, in contrast
to a maleic homopolymer which showed no oxygen absorption whatsoever.
However, the molecular weight is such that the isopropyl acetate
telogen moiety could have accounted for a large part of the oxygen
take-up.  At this stage of the investigation therefore the biode-
gradability of this particular example of the products described in
Netherlands Application 7205685 must be regarded as questionable
(Table 11).
Two other polymeric materials gave indications of being at least
partly biodegradable.  One of these, coded 102-834, is stated to be
a starch derivative.  Its chelation curve is shown in Figure 48, and
its detergency performance in Table 6a, items 51 and 52.  The other
material coded 100-821 was not identified by the supplier.  The de-
tergency screening data (Table 6a, items 60-63) were not especially
promising.

G.   FORMULATIONS BASED ON NON-NITROGENOUS MONOMERIC BUILDERS
Data on the more important monomeric builders tested in the earlier
stages of the program are shown in Table 7.  Diglycollic acid
(coded 38-279) showed moderate promise as a detergency builder,
and was biodegradable (Table 11).  The supplier, however, indicated
that it posed a toxicity problem so it was not studied further.
Item 13, mellitic acid (coded 74-606) is one of a group of similar
compounds described as builders in a series of recent patents.
Although promising, this compound was not studied further because
of poor availability.  Item 15, the furan derivative coded 76-620,
had good building action but failed the biodegradability test
(Table 11).
                                  41

-------
 Of the other materials,  citric acid was  studied most  extensively.
 As is evident from the data it has  proved  to  be particularly effec-
 tive when used with about 20% of a  high  ratio silicate.  Under our
 conditions of concentration and water  hardness a minimum of about
 30% citrate appears to be necessary to get maximum effect.  This is
 evidenced abundantly in the table.   The  silicate citrate combination
 is most effective with the fatty alcohol ethoxylate nonionics
 (Item 22), certain ether carboxylates  (Item 31), and  the sulfo zwit-
 terionics (Items  35 and 36).   The latter formulations dry very well
 as shown in Table 8, and the nonionic  formulation  can be made into
 a satisfactory liquid as shown in Table  8-A.
 Later in the program the builder carboxymethyl oxysuccinate  (CMOS
 coded 96-789)  was studied extensively.  The screening data shown in
 Table 7a indicate that it is  a builder for both anionic and non-
 ionic surfactant  types.   It also proved  to be biodegradable, non-
 toxic to aquatic  organisms and without effect on algal growth.
 Further data on CMOS built compositions  are shown  in  Figures 11-12
 and 33-34.   When  used at the  30% level with IAS, full effectiveness
 of the detergent  is reached at .3%  concentration.
 A 20/8/1/30/41 formulation of LAS and  CMOS was bundle tested against
 AATCCWOB at two different concentrations,  .15% and .3%.  At  .15%
 the panel  preferred AATCCWOB  by a margin of 14 to  5,  a significant
 difference  supported by  the reflectance  readings.   At .3% the
 CMOS was preferred  by a  score of 10.65 to  7.35, a  non-significant
 difference  also supported by  the reflectance  data.
 Several  citrate compositions  were tested extensively, based on the
 promising results of the  screening  tests shown in  Table 7.  These
were based  on  surfactants  other than LAS.   Three of these composi-
 tions were  solids,  all containing 30%  sodium  citrate  and 20% silicate
                                 42

-------
and having the proportions 20/20/1/30/29.  Formulation 64-1 used an
ether carboxylate surfactant coded 60-486.  Formulation 64-2 used a
sulfozwitterionic surfactant coded 54-433, and Formulation 67-1
another sulfozwitterionic coded 42-348.  A liquid composition,
listed as item #1 in Table 8a, was also prepared for further testing.
Formulations 64-1 and 64-2 were tested against the two control de-
tergents at various concentrations and water hardnesses.  All five
test procedures (soils) as outlined in Appendix B were used.  For
quick reference the procedures are:  #1 Empa soil single cycle;
#2 Colgate soil single cycle; #3 Spangler soil multicycle; #4 Vacuum
cleaner dry soil multicycle; #5 Vacuum cleaner sebum or oily soil
multicycle.  The results are shown in Tables 7b and 7c.  These for-
mulations 64-1 and 64-2 were bundle tested against the AHAM deter-
gent at .2% concentration in Rockville tap water.  The panels rated
64-1 equal to the control detergent, but 64-2 was rated inferior,
largely due to a slight yellowing effect.  Details of these tests
are given in Appendix B.
Formulation 64-1 was chosen for one of the two chronic aquatic toxi-
city studies made during the course of the program.  The other study
was made on the representative high-phosphate detergent AATCCWOB.
Both studies are reported together as Appendix E.  The 64-1 formula-
tion appears to be no more harmful to aquatic life than the high-
phosphate material.

H.   WASHING WITH ION EXCHANGE RESINS
Pata on the ion exchange resin washing experiments outlined in the
previous section of this report are presented qualitatively rather
than in tabular form.
                                43

-------
When given adequate time to soften the water the resins both performed
very well, enabling the unbuilt formulations to wash as well as in
distilled water and as well as the corresponding phosphate-built de-
tergents in hard water.  The Dowex was quite slow, requiring almost
an hour to soften the water and effect the washing.  The Amber lite
was more rapid in its action requiring only 30 minutes to produce
the full effect.  Further tests using multicycle procedures on vacuum
cleaner soils gave essentially similar results.  The ion exchange resin
facilitated soil removal but required considerable time to exert its
effect.
It is evident that a cation exchanger which worked more rapidly than
the two that were tried could probably provide a practical washing
system.  Faster acting resins might be made by increasing the bead
porosity and decreasing its dimension, by making the resin in fib-
rous form, etc.  The manner in which the resin is deployed in the
                                                  ...,  ij-t
bath could also be altered to increase the rate of Ca   removal.
Circulation of the wash liquor through a bag of beads is obviously
not optimal.
                                   44

-------
                              DISCUSSION

The various possibilities for developing satisfactory phosphate-
free detergent formulations are conveniently discussed according to
the classification scheme used in the previous section, i.e. eight
different composition categories and seven different categories of
performance or properties.

A.   UNBUILT SURFACTANTS
The data indicate that synergy among two or more surfactants with re-
gard to soil removing power is a very real thing.  A formulation con-
taining in the range of 40% total surfactant and no significant
quantity of builder appears able to perform reasonably well at
practical concentrations, provided the surfactant mixture is suitably
chosen.  Possibly the best evidence of this is provided by the com-
mercial detergents D (Code 104-855) and E (code 96-782).  Added evi-
dence is provided by the laboratory performance of the commercial
detergent extract coded 32-237.
Single surfactants such as LAS, FAEN or the experimental D-116
(code 90-730) appear less effective than the mixtures, although limit-
ed work with the sulfonated zwitterionics indicates that they might
prove sufficiently effective.  They are at present costly, however,
and more a specialty than a bulk item.
                                   45

-------
The soap-LSD combinations fall into a special category.  To give
effective soil removal in hard water a high concentration is needed,
which makes the economics seem unattractive.  Furthermore, as shown
in Table 13, although the LSD does lower the amount of undesirable
residue left on the  fabric  it does not lower it to the level expected
by consumers accustomed to  phosphate containing detergents.  It
should be noted that the soil removing power of these materials is
very high when used  in sufficient concentration.

B.   CARBONATE-SILICATE FORMULATIONS
A high carbonate content certainly increases the soil removal power
of certain surfactants and  surfactant mixtures.  It is objectionable,
however, in causing  rapid build up of solid residues on the fabric
when used in hard water.  A relatively low carbonate content, in the
range of 20%, is correspondingly less objectionable but may not con-
tribute enough extra washing power to be worthwhile  (cf Figures 21
and 22).
The high ratio silicates appear to have some building power for cer-
tain surfactants but not for others.  They also appear to be syner-
gistic with certain  other builders, notably citrate as discussed
below.  Silicates do not appear to have anywhere near the adverse
effects on fabric that carbonate has and are unobjectionable in
other respects as long as the ratio of silica to soda is in the
range of 2:1 or higher.  Evidence of their effectiveness in appro-
priate formulations  is provided by commercial detergent C (coded 96-
783)  in which silicate appears to be the only builder present in
significant quantity.
                                  46

-------
C.   NTA FORMULATIONS
The present studies have confirmed the virtues of NTA,  as evidenced
by all the data.  It is an excellent builder for all surfactants
tested, including the large tonnage inexpensive surfactants now used
in phosphate formulations.  Investigation of some possible disad-
vantages of NTA, reported in the technical literature and to a cer-
tain extent publicized, has not been within the scope of this pro-
gram.

D.   SAND FORMUIATIONS
To the extent that it has been tested SAND is a good builder of de-
tergency, similar in this respect to NTA or phosphate.
The similarity in structure between SAND and NTA, and the fact that
SAND can in theory be converted to NTA by a simple hydrolysis reac-
tion, would make SAND subject to the objections that have been raised
against NTA.  It would presumably be necessary to prove that these
objections were not valid in the case of SAND, a difficult and time-
consuming task outside the scope of this program.

E.   SHIM (HEIDA) FORMUIATIONS
SHIM is an excellent builder for the detergency of all surfactants
tested, in the same class as phosphate and NTA.  It is readily bio-
degradable and fully satisfactory with regard to biostimulation and
acute aquatic toxicity.  SHIM is sufficiently different from NTA
in chemical composition so that the objections raised against NTA
could not legitimately be translated as applicable to SHIM.  Its
toxicity is close to the limits recommended by FDA and Consumer
Products Safety Commission, and more extensive work would have to
                                 47

-------
 be done on SHIM formulations before they could be cleared in this
 regard.  SHIM may also be difficult to formulate into a satisfactorily
 storable solid detergent although it can readily be formulated to
 liquids.
                                                         l
 F.   FORMULATIONS BASED ON POLYMERIC BUILDERS
 None of the polymeric builders tested provide the rapid biodegrad-
 ability characteristic of the "soft" surfactants and some of the mono-
 mer ic builders.  Several, notably the acrylics and maleics,  have
 outstanding building action for the conventional tonnage surfactants.
 It seems to be the general rule,  however, that building effect must
 be traded off against biodegradability.  The best compromise in this
 regard that we have seen so far is the POCNa hydroxylated acrylic
 polymer (code 104-860).  The formulation based on LAS surfactant
 and containing 50% of this builder gave satisfactory laundering per-
 formance at concentrations of 0.2% or higher.  Two other polymeric
 builders show promise of simultaneously meeting both the launder-
 ability and biodegradability requirements.  These are the very low
 molecular weight acrylic (code 100-823) and the maleic telomer
 (code 106-866).  Considerably more work would be required on both
 these products, however,  before a final judgment on their overall
satisfaction could be rendered.
                                                       1 ",
 Polymeric builders in general appear to be biologically inert:  non-
 toxic to aquatic life and non-stimulating to algal growth.  This
 characteristic extends to their lack of biodegradability.
                                  48

-------
G.   FORMULATIONS BASED ON NON-NITROGENOUS MONOMERIC BUILDERS
The two non-nitrogenous monomeric builders that appear as promising
replacements for phosphate are citric acid and CMOS,  Of these
citric acid is by far the more thoroughly explored.  The detergency
building action of citrate varies considerably from surfactant to
surfactant as might be expected of a relatively weak chelating agent
(cf. Figure 47).  Formulation 64-1 shows that with a suitable sur-
factant citrate can provide reasonably satisfactory launderability.
It is highly probable that a synergistic mixture of surfactants could
also be satisfactorily built with citrate.  The only citrate built
commercial- detergent tested (Detergent 0, coded 90-279, Figures 35-36)
was a European product designed for European washing conditions.
There is at least one widely used citrate built detergent in the
phosphate-free market in the U.S.A.  Citrate has the great advantage
of being completely unobjectionable from the ecological and health
hazard standpoints.
CMOS appears to have the same advantages as citrate, and to be some-
what stronger with regard to both sequestration (cf. Figure 47) and
building action.  It gives better results than citrate as a builder
for LAS.  Time did not permit complete testing of CMOS with regard
to all the property categories, but on the basis of evidence at
hand it must be regarded as a serious contender in the phosphate-
substitute competition.

H.   WASHING WITH ION EXCHANGE RESINS
From the environmental point of view a washing system based on ion
exchange resins is close to ideal.  No soluble builder goes down
the drain.  Since all acceptable builders are visualized as being
biodegradable, any combination of surfactant and sequestering
builder would increase the BOD load on the sewage disposal systems
                                  49

-------
 and/or  the  streams  into which  it  flowed.   In the  ion exchange system
 the  surfactant would  be the  only  source of significant BOD.  The only
 product which might seem  to  require  special disposal is calcium chlo-
 ride resulting from regeneration  of  the resin.  However the calcium
 is simply that which  was  removed  from the  laundry's water supply, and
 the  chloride  is  counterion to  the sodium given up by the resin in the
 softening step.   The  only net  addition to  the watercourse in this pro-
 cess is the sodium  chloride  used  in  regenerating  the resin.
Although  we believe the ion-exchange resin system to be very promising
 other priorities in the program precluded  its further exploration.
 Successful  further  development would most  probably come from improve-
ments in  the  resin, and the  form  and manner in which it is used.
 Such development would seem  to be the province of researchers and
manufacturers of cation exchange  resins.   Detergent manufacturers
 and  formulators  would also have to contribute, however, since com-
patibility  with  minor adjuvants of the formulation would have to be
worked  out.   Similarly, much new  data would have  to be elaborated on
 the  detersive power of various surfactants and surfactant mixtures
 in softened water.  Finally, the  various difficulties that are in-
evitably  involved when introducing a new process  to the consumer
would have  to be worked out.   The projected ultimate advantages of
the  process might nevertheless be worth any introductory difficulties.
In deciding which of  the  formulations developed in this program and
discussed above  might be  most  promising it is of  interest to see
what  the  soap and detergent  industry has introduced into the phosphate-
free  market since the start  of the program.   The  first phosphate
substitute was NTA, no longer  being  used in the U.S.A. because the
hazard  question  has not (as  of this  writing)  been definitely an-
swered.  Some high  carbonate (more than 45%)  formulations have been,
and are still being marketed.  A  considerable number of low
                                   50

-------
carbonate (20-25%) formulations are being marketed, some of which con-
tain about an equal amount of silicate.  Some citrate formulations
have appeared, including some in which the citrate is augmented by
carbonate and/or silicate.
A final important group includes fonnuktions consisting essentially
of unbuilt surfactants or surfactants built only with silicate.  To
the writers' knowledge no polymer-built formulations have been intro-
duced in significant quantity,  nor have there appeared any formulations
built with nitrogenous or non-nitrogenous monomeric builders other
than citrate.  There also seems to have been little increase in the
use of soap or soap-based compositions for heavy duty household
laundering in the phosphate-free jurisdictions.  It is of little
profit to speculate on the reasons for this situation.  There is no
doubt that costs play an important role.   The leading surfactants
are themselves relatively inexpensive.  If 50 parts of surfactant
alone will do as good a job as  20 parts surfactant plus 30 parts
builder, then the builder must  be less costly than the surfactant
to justify its use.  Provided that performance is adequate the choice
among formulations, whether they consist of surfactants alone or
surfactant-builder combinations, depends largely on overall cost ef-
ficiency.  Other economic and technical factors, however, also enter
into consideration.
During the three year course of this program the rate at which patents
have been issued on phosphate-free detergent compositions has in-
creased greatly; and at the present writing it has not started to
diminish.  Perusal of these patents, both U.S.A. and foreign, has
been of obvious value in conducting this program, and in some in-
stances (e.g. POCNa and the maleic telomer) has led to some very
promising formulations which might otherwise never have been made or
                                     51

-------
tested.  A selected list of recent patents, classified according to
the outline used in this report, is included as Appendix D.  In
almost all citations the Chemical Abstracts (CA) reference as well
as the patent number is given to facilitate retrieval.
                                    52

-------
                                          Table 1.  DETERGENCY OF SURFACTANTS WITHOUT BUILDER,
                                                          .3%, 4 washes, 200 ppm water
ui
                                                                                                       Delta G Values
Item
No.
1
la
Ib
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Surfactant
Code No.
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
51-104
20-138
68-134
68-134
51-93
43-67
Surfactant Type Proportions
Fatty Alcohol Ethoxylate Nonionic 12/8/1/0/79
ii ti 11 ti ii
it ii ii ii it
" " " 12/8N/1/0/79
12/8D/1/0/79
" " " " 25/8/1/0/66
" " " 20/8/1/0/71
" " " " 20/8GD/1/0/71
11 " " 20/25/1/0/54
" " " 20/25GD/ 1/0/54
11 " " " 20/8D/1/0/71
" " " " 12/20GD/1/0/67
" " " " 25/8/1/0/66
25/8/1/0/66
" " " " 25/8/1/0/66
11 " " " 12/8/1/0/79
" " " " 25/8/1/0/66
" " " " 25/8/1/0/66
Series
Ref. No.
	 a
a
	 a
149-50
122,147
-b
	 c
92-3
92-3
92-3
122,147
102-3
14
-d
21-2
23-4
13
7
Vacuum
Blend
Fabric
4.5
2.1
6.2
5.3
7.2
3.8
5.0
6.7
4.7
7.4
7.2
10.1
4.1
6.0
4.5
7.4
3.5

Soil
Cotton
Fabric
2.5
1.1
4.3
2.1
4.5
1.7
2.2
2.8
1.6
3.1
4.7
8.9
-1.2
-.5
2.7
2.5
.1
1.4
Sebum
Blend
Fabric
4.2
2.4
5.4
5.4
6.3
1.9
2.6
5.1
3.5
3.6
3.4
6.9


-.5
3.1


Soil
Cotton
Fabric
2.0
1.6
3.2
2.3
4.5
-.2
1.1
1.6
-.2
.5
3.2
5.6


.7
1.2


                                                              (Continued)

-------
                                                                                                       Delta G Values
Ul
Table
Item
No.
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
1 (Continued)
Surfactant
Code No. Surfactant Type
51-100 Fatty Alcohol Ethoxylate Nonionic
51-101 " " " "
51-105 " " " "
51-105 M "  "
51-105 " " " "
31-230 Hydroxylated Nonionic
26-191 " "
26-189 " "
43-83
43-83 " fl
20-144 " "
20-145 " "
48-374 Amine Oxide
51-91 Alkane Sulfonate Anionic
22-155 Alpha Olefin Sulfonate Anionic
22-155
74-604
"74-604
68-558
Proportions
25/8/1/0/66
25/8/1/0/66
15/8/1/0/76
25/8/1/0/66
40/8/1/0/66
25/8/1/0/66
25/8/1/0/66
25/8/1/0/66
25/8/1/0/66
25/50/1/0/24
25/8/1/0/66
25/3/1/0/6/5
25/8/1/0/66
25/8/1/0/66
20/8/1/0/71
20/20/1/0/59
20/8/1/0/71
20/20/1/0/59
20/8/1/0/71
Series
Ref. No.
.14
.14
132-3
132-3
132-3
87-8
23-4
23-4
23-4
23-4
11
5
84-5
10
 e
~f
145-6
145-6
124-5
Vacuum
Blend
Fabric
9.0
6.9
3.8
3.9
4.0
10.1
10.0
4,1
2.4
1.6
6.0

8.9

7.4
5.0
9.1
9.0
4.5
Soil
Cotton
Fabric
.3
-.5
1.2
.6
1.0
5.0
5.8
1.7
1.2
.7
2.0
4.2
5.1
3.5
4.7
3.2
4.*
5.0
4.3
Sebum
Blend
Fabric


7.4
4.3
2.7
9.6
5.6
6.1
1.2
2.5


9.9

7.5
5.8
8.3
6.7
3.5
Soil
Cotton
Fabric


5.9
3.9
2.2
3.1
2.7
3.3
.7
K3


3.8

2.8
2.4
4.2
3.1
-2,1
                                                              (Continued)

-------
                                                                                                       Delta G Values
in
Ui
Table
Item
Ko.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
1 (.Continued)
Surfactant
Code No. Surfactant Type
58-471 Ether Sulfate Anionic
62-491
62-491
62-491
6Z-491
62-492
62-492
40-332 Ether Carboxylate Anionic
40-332.
60-486
60-486
60-486
60-486
68-109 Sulfonate Ampholytic
68-108
46-357 Carboay Betaine Zwitterionic
42-348 Sulfo Betaine Zwitterionic
42-348
54-431
Vacuum Soil
k
Proportions
12/8/1/0/79
12/8/1/0/79
20/8/1/0/71
12/20/1/0/67
12/20GD/1/0/67
12/8/1/0/79
20/8/1/0/71
12/8/1/0/79
25/8/1/0/66
12/8/1/0/79
12/20/1/0/79
.-;>* 12/20GD/ 1/0/79
20/20/1/0/59
25/8/1/0/66
25/8/1/0/66
25/8/1/0/66
25/8/1/0/66
20/20/1/0/59
25/8/170/66
Series
Ref. No.
106-7
104-5
104-5
102-3
102-3
104-5
104-5
62-3
62'3
106-7
102-3
102-3
128-9
15
87-8
84-5
84-5
8
87-8
Blend
Fabric
4.8
3.9
4.1
6.4
9.2
4.0
3.9
6.7
4.6
2.8
7.8
7.0
1.5
4.1
5.5
3.3
1.4
3.2
4.5
Cotton
Fabric
3.6
1.9
2.2
5.2
4.2
1.6
1.8
1.9
2,1
1.2
6,2
5.5
.6
1.7
2.4
1.7
-.2
.8
2.1
Sebum
Blend
Fabric
2.7
3.5
4.0
7.8
9.0
4.8
4.3
8.1
3.7
6.4
10.0
8.0
2.8

12,3
3.9
4.4
3.5
5.3
Soil
Cotton
Fabric
.5
1.6
1.6
3.6
6.4
1.6
1.1
1.9
-.6
,5
4.9
3.9
-.1

3.5
.8
-.2
1.4
.6
                                                              (Continued)

-------
                                                                                                     Delta G Values
Ui
Table ]
Item
No.
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
a * t
L (Continued)
Surfactant
Code No. Surfactant Type
54-433
54-433
32r-237
32-237
32-237
34-249
34-249
34-249
34-249
34-249
34-249
34-249
38-282
70-560
20-146
74-594
ive. of 14: 1
Sulf o Betaine Zwitterionic
11 i H
Commercial Detergent Extract
ii ii M
II II H
Linear Alkylaryl Sulfonate (LAS)

ii ii ii ii


it ii it ii

Commercial Detergent, Approx.
70 nonionic, 20 amine soap
Commercial Detergent, Approx.
20 nonionic, 7 soap
Mixture 85 low titer soap,
15 silicate D
Mixture soap, lime-dispersing
anionic, silicate ER 544-15 1A
>  avg. of 4; c = avg. of 5; d = SM
Vacuum Soil
k
Proportions
25/8/1/0/66
20/20/1/0/59
25/8/1/0/66
25/50/1/0/24
25/8/3/0/64
25/8/1/0/66
20/8/1/0/71
20/8GD/1/0/71
20/25/1/0/54
20/25GD/1/0/54
20/20/1/0/59
20/20GD/ 1/0/59
as is
as is
as is
as is
'g. series 2, 4, 6,
Series
Ref. No.
87-8
130-1
28-9
28-9
28-9
--1
-J
92-3
92-3
92-3
94-5
94-5
62-3
126-7
142-3
142-3
11, 13, 14;
Blend
Fabric
.9
1.6
4.1
2.9
2.9
8.2
7.8
8.8
6.0
7.3
10.7
10.1
6.4
2.4
.1
-.2
e < avg.
Cotton
Fabric
-.4
2.9
.9
-.1
.7
4.4
4.5
4.4
3.7
4.7
5.4
4,2
5.4
6.1
-.3
-1.3
of 7; f -
Sebum
Blend
Fabric
3.9
5.5
1.7
.9
1.3
7.0
6.8
7.3
4.9
6.2
7.0
6.3
6.8
2.2
0
-.6
avg. of 3;
Soil
Cotton
Fabric
-.3
2.1
-.6
-.4
-.1
4.7
4.7
3.8
2.9
3.2
5.1
5.0
5.2
4.5
.3
-1.6

     g  avg. of  2; h  
     k = % surfactant/
 alcohol extract of a leading commercial detergent; i  avg. of 9; J  avg. of 3.
%  silicate/ % NaCMC/ % builder/ %  sodium sulfate.

-------
TABLE 1A. DETERGENCY  OF SURFACTANTS WITHOUT BUILDER
         3XSPANGLER  SOIL*3 WASHES* 200 PPM WATER
                                                   DELTA  W
ITEM
NO.
71
72
73
74
o, 75
-4
76
77
78
79
80
81
82
SURFACTANT
CODE NO. SURFACTANT TYPE
90-730
90-730
90-730
68-127
68-127
68-127
20-145
20-145
102-836
102-836
34-249
34-249
ANIONIC SULFONATE
ANIONIC SULFONATE
ANIONIC SULFONATE
FATTY ALCOHOL ETHOXYLATE
NONIONIC (FAEN)
FAEN
FAEN
HYDROXYLATED NONIONIC
HYDROXYLATED NONIONIC
FATTY ACID DIETHANOLAMINE
CON DEN SATE + FAEN
FATTY ACID DIETHANOLAMINE
CON DEN SATE + FAEN
LAS
LAS
PROPORTIONS
10/7/1/0/82
15/7/1/0/73
27/8/1/0/64
12/8/1/0/79
12/20/1/0/67
27/8/1/0/64
20/8/1/0/71
20/20/1/0/59
15+5/8/1/0/71
15+5/20/1/0/59
20/8/1/0/71
25/8/1/0/66
SERIES BLEND
REF.NO. FABRIC
213
213
231*234*239
215*233*235*238
244*245*249*251
238
234
211
211
246
246
236* 244* 245* 249
251
214*224*237
7.5
5*8
5.0
10*4
10*4
6.9
14.7
17.4
5.0
3*6
6.9
4.0
COTTON
FABRIC
3.4
1.3
1.6
7.7
5.0
3.4
8.5
6.4
0*3
-1.4
3.8
2.2

-------
TABLE 1A. (CONTINUED)
                                                                     DELTA  V
ITEM SURFACTANT
NO. CODE NO. SURFACTANT TYPE
83
84
85
86
u. 87
00
34-249
34-249
86-706
86-707
86-708
LAS
LAS
SOAP-LIME SOAP DI SPERSER
ER AF569- 144-1
SOAP-LIME SOAP DI SPERSER
ER AF569- 144-2
SOAP-LIME SOAP DI SPERSER
ER AF569-144-3
PROPORTIONS
25/20/1/0/54
27/8/1/0/64
AS IS
AS IS
AS IS
SERIES
REF..NO-
237
234* 239
216
216
216
BLEND COTTON
FABRIC FABRIC
3.6 0.6
4*9 2.2
-0.5 -0.1
-0.4 -2.2
-0.1 -1.7

-------
                                     Table 2.  DETERGENCY  OF  SURFACTANT -  CARBONATE FORMULATIONS,

                                                         .37., 4 washes,  200  ppm water
Ui
vo
                                                                                                      Delta  G  Values
Vacuum Soil
Item
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
a =
Surfactant
Code No.
68-134
68-134
51-93
51-101
51-105
68-127
68-127
26-191
26-189
43-83
32-237
34-249
34-249
51-105
51-105
36-278
36-277
36-276
avg. of 3; b =
Surfactant Type Proportions
Fatty Alcohol Ethoxylate Nonionic 25/8/1/66/0
12/8/1/66/13
" " " 25/8/1/66/0
25/8/1/66/0
" " " " 25/8/1/66/0
" " " " 25/8/1/66/0
" " " " 12/8/1/66/13
Hydroxylated Nonionic 25/8/1/66/0
" " 25/8/1/66/0
25/8/1/66/0
Commercial Detergent Extract 25/8/1/66/0
Linear Alkylaryl Sulfonate (LAS) 20/8/1/35/36
25/8/1/60/6
Fatty Alcohol Ethoxylate 12/8/2/66/12
" 12/20/2/66
Low Titer Soap, Nonionic Mixture 20/15/8/1/36/20
40/15/8/1/36/0
High " " " " 40/15/8/1/36/0
alcohol extract of a leading commercial detergent.
Series
Ref. No.
23-4
23-4
19-20
19-20
19-20
23-4
a
23-4
23-4
23-4
28-9
120-1
134
30-2
30-2
42-3
42-3
42-3

Blend
Fabric
8.3
5.2
.7
.3
1.6
1.7
3.5
3.6
-.7
2.6
1.2
4.5

4.3
.5
1.8
2.0
.1

Cotton
Fabric
1.7
.8
1.1
1.5
.9
-.8
.5
1.0
-.2
-.8
-.2
4.9

-.1
-2.3
1.1
.3
-.1

Sebum
Blend
Fabric
.9
1.6
1.3
.5
1.3
0
2.8
1.3
1.8
2.7
.4
4.3
3.5
5.3
4.7
4.8
3.8
.3

Soil
Cotton
Fabric
.1
.5
-.6
-.6
-.5
0
1.8
1.2
2.7
.7
-1.1
3.9
3.4
1.0
1.3
1.2
.4
.8


-------
Table J. UKILRGEMCY OF SUEFACTAKT - KTA POSMJIAT1O5S,
.31, 4 vashes, 200 ppa water
Item
Ko.
1
2
3
4
5
6
7
ov 8
o
9
Surfactant
Code Bo.
51-91
34-249
68-558
68-109
68-134
68-127
22-155
20-138
51-93

Surfactant Type Proportions
Allran* s%| frn% afp Anionic 20/8/1/30/41
Alkylaryl Snlfonate Anionic (IAS) 20/8/1/30/41
Alpha Olefin Sulfonate Anionic 20/8/1/30/41
Snlfntartt Aa^nlyfi r ?*>/fl/1/lQ/36
Fvt*7 Mrflitol Fthfwylflte Wtmionlr 25/8/1/10/^6
12/8/1/30/49
Alpha Olefin Sulfonate 2O/8/1/30/41
Fatty Alcohol F* *MP"y l^f** ^%?n1onic 25/8/1/30/36
25/8/1/30/36
Series
8ef. Ho.
100-1
a
124-5
21-2
21-2
72-3
a
a
	 a
Yacuua
Blend
Fabric
1.1
.7
-1.7
.2
2.0
-.3
-1.5
-2.5
-3.2
Delta G Values
i Soil
Cotton
Fabric
1.0
1.2
-.6
-.1
.1
.9
-.9
-4.0
-1.9
Sebua Soil
Blend
Fabric
.8
.7
-1.8
.2
-1.2
1.7
-.9
1.5
Gotten
Fabric
.6
.7
-1.2
1.1
.6
.1
-1.7
.6
a * avg. of 3.

-------
Water
ppn
50
50
50
50
125
125
125
125
200
200
200
200
330
300
300
300
Tab
Tut gill a ti on
CflHwmt r -at ion
percent
.10
.15
.20
.30
.10
.15
.20
.30
.10
.15
.20
.30
.10
.15
.20
.30
I ^ to v MKiuHrfv WJ Y OF
AT VAHVT1K
Soil - Vacant
f fivATlC ~ " ii^^^r
Delta G
-.5
-.5
-1.7
-1.6
.6
-.1
-.1
-.6
.4
-1.0
.6
-1.9
.8
.3
-3.3
-.2
HI& - AIPS&. 01EFIK SOLFCEA2E FCKJflJIATICK
Soil - Vacuoa
Fabric -.Cotton
Delta G
.1
-.2
-.8
-.3
.9
-.7
-1.0
-1.0
1.3
.7
.6
-.5
.5
.7
-3.4
-.2
Soil - Sebua
Fabric - Blend
Delta G
-.1
-.4
-.3
.2
3.0
.9
.3
-.6
7.0
3.6
.4
-.6
3.7
4.9
.9
-.8
Soil - Sebua
Fabric - Cotton
Delta G
.8
-1.2
-.8
-.2
1.8
-.2
-.4
-.6
4.0
1.4
-.4
-1.2
.8
1.1
.2
0
a * Alpha Olefin Solfonate Code 22-155, Formulation proportion 20/8/1/30/41

-------
N>
                                     Table 4.   DETERGENCY OF SURFACTANT -  SAND FORMULATIONS,
                                                       .3%,  4 washes,  200  ppm water
                                                                                                    Delta G Values
Vacuum Soil
Item
No.
1
2
3
4
5
6
7
8
Surfactant
Code No.
68-127
68-127
68-127
62-491
22-155
60-486
51-91
34-249
Surfactant Type
Fatty Alcohol Ethozylate Nonionic
ii ii ii ii
ii ii it ii
Ether Sulfate Anionic
Alpha Olefin Sulfonate Anionic
Ether Carboxylate Anionic
Alkane Sulfonate Anionic
LAS Anionic
Proportions
12/8/1/30/49
20/8/1/30/41
12/8/1/50/29
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
Series
Ref. No.
52-3
117-8
	 a
117-8
-b
117-8
117-8
	 c
Blend
Fabric
.2
-1.4
.5
-.3
_ o
-2.0
2.2
3.9
Cotton
Fabric
-.5
-1.2
*  J
-.2
-.5
-2.3
.8
2.2
Sebum Soil
Blend
Fabric
.9
-1.0
.5
-.7
.3
-2.4
1.4
3.0
Cotton
Fabric
.6
-4.1
.3
-3.9
-1.5
-5.1
-1.7
3.2
     a 
avg. of 2; b = avg. of 3; c = avg. of 4.

-------
Ul
                                       Table 5.  DETERGENCY OF SURFACTANT - SHIM FORMULATIONS,
                                                          .3%, 4 washes, 200 ppm water
                                                                                                      Delta G Values
Vacuum Soil
Item
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
Surfactant
Code No. Surfactant Type
68-127 Fatty Alcohol Ethoxylate Nonionic
68-127 " " " "
68-558 Alpha Olefin Sulfonate Anionic
22-155
74-604 " " " "
60-486 Ether Carboxylate Anionic
40-332
78-634 " " "
78-633 " " "
78-635 Fatty Alkyl Sulfate Anionic
58-471 Ether Sulfate Anionic
34-249 Alkylaryl Sulfonate Anionic (LAS)
34-249
Proportions
12/8/1/30/49
12/8/1/50/29
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
12/8/1/30/49
20/8/1/30/ b
20/8/l/30/b
20/8/1/30/ b
20/8/1/30/ b
12/8/1/30/49
20/8/1/30/41
25/8/1/50/16
Series
Ref. No.
	 a
89-90
124-5
	 a
145-6
106-7
135-6
155-6
155-6
155-6
106-7
98-9
89-90
Blend
Fabric
.2
.4
.4
-.2
.7
-1.1
-.7
.fr
.4
-.3
1.3
1.6
1.2
Cotton
Fabric
-.3
-1.3
.3
.5
.6
-.7
-.9
.2
.1
0
1.5
2.4
1.4
Sebum Soil
Blend
Fabric
-1.4
-.7
-.6
-.1
1.2
-1.5
0
1.4
1.0
.6
1.3
1.6
.6
Cotton
Fabric
-1.5
.1
-.9
-.3
0
-2.6
-.9
.4
.6
.8
-.4
1.0
1.2
      a * avg. of 3; b - liquid formulation: water plus 10% hydro trope.

-------
                           Table 6.   DETERGENCY OF POLYMERIC BUILDER -  SURFACTANT FORMULATIONS,
                                                   .37,,  4 washes,  200 ppm water
                                                                                                Delta G Values
Vacuum Soil
Item Builder Type
No. and Code
1 Acrylic 43-65
2
3 " 20-141
4 Maleic 40-310
C II II
6
-j H ti
8 "
g 11 it
10 Carbohydrate
Surfactant Type and Code
Sulfo Ampholytic 68-109
Fatty Alcohol Ethoxylate
Nonionic 68-134
Sulfo Ampholytic 68-109
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
ti ii
ti ii

Proportions
25/8/1/30/36
25/8/1/30/36
25/8/1/30/36
12/8/1/30/49
12/8/1/3/76
12/8/1/0/79
25/8/1/30/36
25/8/1/3/63
25/8/1/0/66

Series
Ref. No.
21-2
21-2
21-2
52-3
77-8
77-8
52-3
77-8
77-8

Blend
Fabric
3.9
3.7
5.7
-2.7
1.4
2.4
-.4
3.9
5.7

Cotton
Fabric
3.4
2.3
4.5
-2.1
2.1
3.3
-.5
3.1
4.2

Sebum Soil
Blend
Fabric
3.9
-.4
7.2
-2.1
3.0
3.4
0
5.1
6.1

Cotton
Fabric
1.9
.7
1.9
-1.1
.3
1.1
.4
2.7
3.8

          74-602

11     Carbohydrate
          74-602
Fatty Alcohol Ethoxylate
   Nonionic 68-127
                            25/8/1/50/16       147-8
                                                      12/8/1/30/49       147-8
3.9
4.1
2.5
2.6
2.1
3.6
2.3
1.9
12     Carbohydrate
          66-530
Alpha Olefin Sulfonate
   22-155
                                                      20/8/1/30/41       122-3
1.8
2.2
2.9
2.7

-------
                                                                                                       Delta G Values
01
Table 6 (Continued)
Item Builder Type
No. and Code
13 Copolymer 66-532
14
15 " "
16 " 66-533
17
18
19 " 58-466
20 " 58-467
21
22
23
24
Surfactant Type and Code
Fatty Alcohol Ethoxylate
Nonionic 68-127
Alpha Olefin Sulfonate
22-155
LAS 34-249
Fatty Alcohol Ethoxylate
Nonionic 68-127
Alpha Olefin Sulfonate
22-155
LAS 34-249
ii ii
it ii
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Alpha Olefin Sulfonate
22-155
Alpha Olefin Sulfonate
22-155
Proportions
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
12/8/1/30/49
12 /8N/ 1/30/49
20/8/1/30/41
20/8N/1/30/41
Series
Ref. No.
122-3
122-3
122-3
122-3
122-3
122-3
98-9
98-9
149-50
149-50
151-2
151-2
Vacuum
Blend
Fabric
2.2
4.5
5.7
-.2
1.0
1.6
2.0
2.5
.9
.7
.1
.3
Soil
Cotton
Fabric
1.6
4.6
4.1
-.4
.5
1.7
1.3
.7
-.6
-.2
.1
.8
Sebum
Blend
Fabric
2.7
3.7
5.3
-1.1
.8
2.0
2.2
1.6
1.6
-.2
.9
.4
Soil
Cotton
Fabric
1.9
3.1
5.0
.4
1.5
2.3
2.1
2.3
-.6
-.4
.1
.2

-------
              TABLE 6A  DETERGEMCY OF POLYMERIC BUILDER-SURFACTANT  FORMULATIONS
                            3X*SPANGLER SOIL*3 WASHES*200PPM  WATER
   ITEM
    NO.  BUILDER TYPE AND COPE
SURFACTANT TYPE AND CODE
                        DELTA   W
              SERIES   BLENDCOTTON
PROPORTIONS    REF.NO. FABRIC  FABRIC
ON
25
26
27
28
89
30
31
32
33


34


35


36


ACRYLIC
ACRYLIC
ACRYLIC
ACRYLIC
ACRYLI C
ACRYLIC
ACRYLIC
ACRYLIC
HYDROXYLATED
ACRYLIC
CO POLYMER
HYDROXYLATED
ACRYLIC
CO POLYMER
HYLi.OXYLATED
ACRYLIC
CO POLYMER
HYTROXYLATED
ACHYLIC
CO POLYMER
92-745
92-745
100-823
100-823
100-823
100-823
100-824
100-824
104-860


104-860


104-860


104-860


LAS
FAEN
LAS
LAS
FAEN
FAEN
LAS
FAEN
LAS


LAS


FAEN.


FAEN


34-249
68-127
34-249
34-249
68-127
68-127
34-249
68-127
34-249


34-249


68-127


68-127


20/8/1/30/41
12/8/1/30/49
20/8/1/30/41
20/8/1/50/21
12/8/1/30/49
12/8/1/50/29
2O/8/1/30/41
12/8/1/30/49
20/8/1/30/49


20/8/1/50/29


12/8/1/30/49


12/8/1/50/29


236
215*235
244
245
244
245
244
244
251


251


251


251


1.4
1.8
3.3
1*6
7.7
2.5
2.9
3.6
2.9


2*7


7.5


4.8


1*0
-1.4
1*5
0.1
3*8
1.7
1.2
2.0
1.2


0.8


7.7


5.5



-------
TABLE 6A. (CONTINUED)
                                                                         DELTA  W
[TEM
NO.
37
38
39
40
4\

42

43

44

45
46
47
48
*
BUILDER TYPE AND CODE
MALEIC TELOMER
MALEIC TELOMER
MALEIC TELOMER
MALEIC TELOMER
MALEIC HOMO- 
POLYMER
MALEIC HOMO- .
POLYMER
MALEIC
CO POLYMER
MALEIC
CO POLYMER
CARBOHYDRATE
CARBOHYDRATE
CARBOHYDRATE
CARBOHYDRATE
106-866
106-866
106-866
106-866
106-870

106-870

86-709

86-709

86-704
86-704
100-822
100-822
SURFACTANT
LAS
LAS
FAEN
FAEN
LAS

FAEN

LAS

FAEN

LAS
FAEN
LAS
LAS
SERIES BLEND
TYPE AND CODE PROPORTIONS REF.NO. FABRIC
34-249
34-249
68-127
68-127 '
34-249

68-127

34-249

68-127

34-249
68-127
34-249
34-249
20/8/1/30/41
20/8/1/50/21
12/8/1/30/49
12/8/1/50/29
20/8/1/30/41

12/8/1/30/49

25/8/1/30/36

12/8/1/30/49

25/8/1/30/36
12/8/1/30/49
20/8/1/30/41
20/8/1/50/21
251
251*
251
251
251

251

214

215

214*
215
244*
245*
0.3
267-0.3
0.5
-0.5
0.3

0.4

1*3

3.9

224 4.7
9.8
249 4.2
249 1.6
COTTON
FAERIC
-0.2
-0.6
0.3
0-0
o.o

-0.6

-0.2

1.1

1.0
6.0
3. 1
-0. 1

-------
               TABLE 6A.  (CONTINUED)
                                                                                          DELTA  V
00
ITEM
NO.
49
50
51
52

53


54


55

56

57

58

59

60
BUILDER TYPE AND CODE SURFACTANT
CARBOHYDRATE
CARBOHYDRATE
CARBOHYDRATE
CARBOHYDRATE
UNIDENTIFIED
CARBOXYLATED
K3LYMER
UN IDENTIFIED
CARPOXYLATED
POLYMER
UNIDENTIFIED
CARBOXYLATED
POLYMER
UNIDENTIFIED
POLYMER
UNIDENTIFIED
POLYMER
UNIDENTIFIED
POLYMER
UNIDENTIFIED
POLYMER
UNIDENTIFIED
100-822
100-622
102-834
102-834

86-705


86-705


86-705

98-806

98-806

98-807

98-807

100-821
FAEN
FAEN
LAS
FAEN

LAS
*

LAS


FAEN

LAS

FAEN

LAS

FAEN

LAS
TYPE AND CODE PROPORTIONS
68-127
68-127
34-249
68-127

34-249


34-249


68-127

34-249

68-127

34-249

68-127

34-249
12/8/
12/8/
20/8/
12/8/
"
25/8/


20/8/


12/8/

1/30/49
1/50/29
1/50/21
1/50/29

1/30/36


1/30/41


1/30/49

20/8/1/30/41

12/8/

20/8/

12/8/

20/8/

1/30/49

1/30/41

1/30/49

1/30/41.
SERIES BLEND
REF.NO. FAPRIC
244* 249
245* 249
245
245

214*224


236


215*235

236

235

236

235

244* 249
4*
3.
2*
3.

1.


5*


5.

1*

5*

1.

3.

3*
6
1
0
2

7


3


8

4

8

8

4

1
COTTON
FABRIC
3.9
3*5
00
1*6

0.5


1*1


1*6

1.4

1*2

1.4

-0.1

4. 1
           FOLYMEh

-------
            TABLE  6A.  CCONTINUED)
ITEM
 NO.  BUILDER TYPE  AND CODE
                                                   DELTA   W
                                         SERIES   BLEND    COTTOM
SURFACTANT TYPE AND CODE  PROPORTIONS    REF.NQ. FAPRIC   FAPRIC
61  UNIDENTIFIED   100-821
    POLYMER

62  UNIDENTIFIED   100-821
    POLYMER

63  UNIDENTIFIED   100-821
    POLYMER
                                      LAS
                                      FAEN
                                      FAEN
             34-249
              68-127
              68-127
20/8/1/50/21    249
5.3
12/8/1/30/49    244*249  4.3
12/8/1/50/29    249
3*8
3.0
        3*4
0.5

-------
Table 7.  DETERGENCY OF MONOMERIC BUILDER - SURFACTANT FORMULATIONS
                        .3%, 4 washes, 200 ppm water
                                                                     Delta 6 Values
Vacuum Soil
Item
No.
1
2
3
4
5
6
7
8
9
10
11
Builder Type
and Code
Diglycollic Acid
38-279
Diglycollic Acid
38-279
Diglycollic Acid
38-279
Diglycollic Acid
38-279
Diglycollic Acid
40-309
Diglycollic Acid
40-309
Oxycarboxylic
Acid 66-541
Oxycarboxylic
Acid 66-541
Oxycarboxylic
AeLd-66-541
Oxycarbbxylic
Acid 74-596
Oxycarboxylic
Acid 74-596
Surfactant Type and Code
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
it it
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
Fatty Alcohol Ethoxylate
Nonionic 68-127
Alpha Olefin Sulfonate
22-155 - -
LAS 34^249
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Proportions
12/8/1/30/49
12/8/1/50/29
25/8/1/30/36
25/8/1/50/16
12/8/1/50/29
25/8/1/50/16 -
20/8D/1/30/41
20/8D/ 1/30/41
20/8D/ 1/30/41
12/8/1/60/19
low pH
12/8/1/60/19
high pH
Series
Ref. No.
45-6
52-3
45-S
52-3
' 52-3
a
122-3
122-3
122-3
137-8
149-50
Blend
Fabric
2.6
5.8
2.6
4.9
2.0
6.1
1.8
4.6
5.6
1.4
3.7
Cotton
Fabric
.2
4.6
2.2
1.8
~3
2*2
1.8
3.5
4.9
- .3
1.6
Sebum Soil
Blend
Fabric
4.2
2.4
6.4
3.8
2.0
5.1
U3
4.7
5.0
2.1
3.5
Cotton
Fabric
1.3
2.0
5.0
2.7
1.3
2.9
2.3
4U
5.7
.a
1.9

-------
Table 7 (Continued)
                                                                                                 Delta G Values
Vacuum Soil
Item
No.
12
13
14
15
16 --
17
18
19
20
21
Builder Type
and Code
Monoe thanolamine
Carbonate 72-589
Mellitic Acid
74-606
Mellitic Acid
74-606
Tetrahydrofuran
Tetracarboxy
Acid 76-620
Tetrahydrofuran
Tetracarboxy
Acid 76-620
Clucohep tonic
Acid 20-151
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Surfactant Type and Code
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
Fatty Alcohol Ethoxylate
Nonionic 8-127
Hydroxylated Nonionic
43-83
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Proportions
12/8/1/60/19
12/8D/1/30/49
25/8D/1/50/16
12/8/1/30/49
25/8/1/50/16
20/20/1/30/29
25/8/1/30/36
25/8/1/30/36
20/20G/1/20/39
20 /20GD/ 1/20/39
Series
Ref, No.
137-8
147-8
147-8
149-50
153-4
128-9
23-4
23-4
94-5
94-5
Blend
Fabric
3.6
4.8
2.7
1.9
1.7
3.6
.4
4.1
1.6
2.5
Cotton
Fabric
2.3
.6
2.2
.1
1.9
1.0
.2
.6
.8
.1
Sebum Soil
Blend
Fabric
1.7
1.7
1.8
1,4
U7
1.4
2.7
1.7
1.3
1.4
Cotton
Fabric
1.1
.9
2.1
.6
3.1
.9
.7
.8
.4
.5

-------
                                                                                                        Delta G Values
to
Table
Item
No.
22

23

24

25

26

27

28

29

30

31

32

/ (.Continued)
Builder Type
and Code
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Vacuum Soil
Surfactant Type and Code
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Ether Sulfate Anionic
62-491
Ether Sulfate Anionic
62-491
Alpha Olefin Sulfonate
Anionic 22-155
Alpha Olefin Sulfonate
Anionic 22-155
Alpha Olefin Sulfonate
Anionic 74-604
Ether Carboxylate Anionic
40-332
Ether Carboxylate Anionic
60-486
Ether Carboxylate Anionic
60-486
Ether Carboxylate Anionic
78-633
Proportions

12/20GD/1/20/47

20/20G/1/30/29

12/20G/1/20/47

12/20GD/1/20/47

20/20G/1/30/29

20/20D/1/30/29

20/20/1/30/29

20/20D/1/30/29

12/20/1/20/47

20/20/1/30/29

20 /20D/ 1/30/29
Series
Ref. No.

102-3

128-9

102-3

102-3

130-1

145-6

145-6

155-6

102-3

128-9

155-6
Blend
Fabric

3.0

-.1

4.0

5.0

.1

1.7

2.6

1.9

3.0

-.1

4.7
Cotton
Fabric

2.7

-.5

3.9

4.8

.7

.2

.1

-.1

3.1

.3

2.4
Sebum Soil
Blend
Fabric

2.2

-.1

6.8

7.5

.6

2.6

2.1

.7

6-1

-2.0

5.9
Cotton
Fabric

2.3

-.5

3.1

3.4

.3

0

0

-.5

3.1

-.6

2.8

-------
                                                                                                          Delta G Values
u>
Table
Item
No.
33
34
35
36
7 (Continued)
Builder Type
and Code
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Surfactant Type and Code Proportions
LAS 34-249 20/20G/1/20/39
" " 20/20GD/1/20/39
Sulfo Zwitterionic 42-348 20/20/1/30/29
11 " 54-433 20/20/1/30/29
Series
Ref. No.
94-5
94-5
	 a
130-1
Vacuum
Blend
Fabric
4.8
4.8
-.1
-.7
Soil
Cotton
Fabric
3.2
2.4
-1.8
-.1
Sebum
Blend
Fabric
3.6
2.0
.2
.7
Soil
Cotton
Fabric
3.5
2.7
-1.5
-.4
       a = avg.  of  2.

-------
    TABLE 7A. DETERQENCY OF MONOMER!C BUILDER-SURFACTANT FORMULATIONS
                  *3X*SPANGLER SOIL*3 WASHES/SOOPPM  WATER
                                                                               DELTA   W
ITEM
NO*
37
38
39
40
41
42
43
44
45
46
47
48
49
50
BUILDER TYPE AND CODE
CMOS
CMOS
CMOS
CMOS
CMOS
CITRIC ACID
CITRIC ACID
CITRIC ACID
CITRIC ACID
CITRIC ACID
CARBOXYETHYL
ACETONE
CARBOXYETHYL
ACETONE
CARBOXYETHYL
ACETONE
CARBOXYETHYL
96-789
96-789
96-789
96-789
96-789
20-1 58
80-158
80-152
20-152
20-152
102-833
102-833
102-833
102-833
SURFACTANT
LAS
LAS
LAS
FAEN
FAEN
LAS
LAS
LAS
FAEN
FAEN
LAS
LAS
FAEN
FAEN
TYPE AND CODE
34-249
34-249
34-249
68-127
68-127
34-249
92-752
34-249
68-187
68-127
34-249
34-249
68-127
68-127
SERIES
PROPORTIONS REF.NO.
20/8/1/30/41
25/8/1/30/36
25/8/1/50/16
12/8/1/30/49
12/8/1/50/29
25/8/1/30/36
25/8/1/30/36
25/20/1/30/24
12/8/1/3C/49
12/20/1/30/37
20/8/1/10/61
20/8/1/50/21
12/8/1/10/69
12/8/1/50/29
S36
837
237
235
238
214
224
237
215
238
245
245
245
245
BLEND
FABRIC
2.0
2.9
0.7
3. 1
2. 1
1.8
2*5
3.2
6*1
7.0
5.9
11.4
10.8
9*4
COTTON
FAEFU C_
0.7
-0.3
-0. 1
1.6
-0.8
1.2
0*1
0.8
3.5
4.4
-1.2
6.8
8.5
5.4
ACETONE

-------
                                                      Table 7B
-j
Ul
     Detergent
                              EFFECT OF CONCENTRATION ON WHITENESS OF SOILED SWATCHES
                        Whiteness Units Lost as Concentration is Decreased (runs 173-196)

                                                 200 ppm Water
                                                   Purapress
 Procedure 1
Concentration
.3%  .2%  .1%
 Procedure 2
Concentration
.3%  .2%  .1%
 Procedure 3
Concentration
.3%  .2%  .1%
 Procedure 4
Concentration
 3*o  + .b  * -L/o
 Procedure 5
Concentration
.3%  .2%  .1%
AATCC
ARAM
66-1 (D)
64-2(M)
0
0
0
0
-.6
.7
6.3
4.5
16.5
19.9
9.4
10.8
o i-o
0 -5
0 9.3
0 5.2
16.6
21.3
16.6
14.6
C
0
0
0
-1.9
.5
1.7
.6
2.1
7.3
4.1
2.5
0
0
0
0
.7
-.4
4.2
.7
5.9
7.2
14.1
6.1
Cotton
AATCC
AEAM
64-l(D)
64-2(M)

0 .4 2.8 0
0 .7 2.5 0
0 2.7 5.7 0
0 -.7 5.4 0

-.1
0
2.2
2.1

7.3
9.6
9.6
7.8
Tap
0 .7
0 .3
0 2.8
0 1.7
Water
10.7
12.6
8.4
7.1

C
0
0
0

.1
1.0
1.6
1.4

2.3
3.4
4.5
3.8

0
0
0
0

-.S
.5
1.4
.9

3.0
4.5
6.4
14.4

Durapress
AATCC
AHA!-!
64-l(D)
64-20-0

AATCC
AHA:-:
64-l'(D)
64-200
0
0
0
0

0 .5 1.2 0
0 -.1 -.3 0
0 .9 5.4 0
0 .4 4.5 0
-1.1
.6
4.9
3.5

-.4
.5
1.4
.4
6.3
8.6
12.1
13.6
C
4.5
5.7
4.S
3.5
0 -.8
0 -.1
0 6.8
0 4.1
otton
0 -.6
0 1.0
0 1.3
0 1.0
3.9
8.4
20.1
14.8

3.1
5.7
7.4
5.6
0
0
0
0

0
0
0
0
-.5
-.7
1.1
.5

-.1
.1
2.1
~  _L
-.5
1.3
3.2
2.3

.6
.1
3,1
2.3
0
0
0
0

0
0
0
0
-.3
-1.3
1.8
-.2

-1.3
-.1
o
 /-
1.3
1.2
2.6
9.5
4.8

-1.8
.4
3.2
5.2

-------
                                    Table 7C

           EFFECT OF WATER HARDNESS ON WHITENESS OF SOILED SWATCHES
Whiteness Readings in Tap Water minus Whiteness Readings  in Hard Water  (200 ppm)
                                 (Series  173-196)

                                    Duraoress
Detergent
AATCC
AHAM
64-l(D)
64-2(M)

AATCC
AHAM
64-l(D)
64-2 (M)
Procedure 1 Procedure 2
Concentration Concentration
.3% .2% .1% .3% .2% .1%
.3
.4
4.8
1.5

.1 0 1.7 .4
1.1 1.9 3.9 .8
2.6 4.4 2.9 .6
1.3 1.4 2.2 -.7
.8
.5
6.2
2.5

.7
.3
1.4
1.0
10.5
11.7
2.1
-.3

3.3
4.7
5.4
2.6
Procedure 3
C or. cen t r a t i on
">./' 97 17
. ->A . f.n . JL/o
~. 7
.3
8.7
4.0
Cotton
1.2
1.5
5.2
4.4
1.1
.9
11.2
5.1

2.5
.8
6.7
5.1
13.0
13.2
5.2
4.6

8.8
8.4
6.2
5.9
Procedure 4
Concentration
. 3% . 2% . 1%
4.4
1.4
1.6
4.2

2.0
1.0
2.0
.8
2,8
2.6
2.2
4.3

1.0
-.1
1.5
2.1
7.0
7.4
2.5
4.4

3,7
4.3
3.4
l.S
Procedure 5
Concentration
 J/'o  *-/:  J_.'n
1.9
1.0
-1.1
-1.2

1.8
1.7
.
. 1.0
.5
1.9
1.3
-.3

2.3
1.3
1.6
.1
6.6
5.6
3.5
.1

6.6
5.8
3.6
o
 -

-------
             TABLE 8.  REPRESENTATIVE DRUM-DRIER FORMULATIONS
                        OF SATISFACTORY CHARACTER8
1.   30 parts NTA; 20 parts alpha olefin sulfonate surfactant 22-155;  I part
     NaCMC; 8 parts silicate; D; 41 parts sodium sulfate (Formulation Ref.  No.
     64-511).
2.   30 parts SAND; 20 parts ether carboxylate surfactant 60-486;  1 part
     NaCMC; 8 parts silicate D; 41 parts sodium sulfate (Formulation Ref.
     No. 64-515).
3.   30 parts SAND; 20 parts ether sulfate surfactant 62-491; 1 part NaCMC;
     8 parts silicate D; 41 parts sodium sulfate (Formulation Ref.  No.  64-514).
4,   30 parts SAND; 15 parts fatty alcohol ethoxylate nonionic surfactant
     68-127; 1 part NaCMC; 8 parts silicate D; 46 parts Na.SO, (Formulation
     Ref. No. 64-516).
5.   30 parts sodium citrate; 20 parts silicate G; 20 parts sulfo zwitterionic
     surfactant 54-433; 1 part NaCMC; 29 parts sodium sulfate (Formulation
     Ref. No. 64-2).
6.   30 parts sodium citrate; 20 parts silicate G; 20 parts sulfo zwitterionic
     surfactant 42-348; 1 part NaCMC; 29 parts sodium sulfate (Formulation Ref.
     No. 67-1).
7.   30 parts sodium citrate; 20 parts silicate G; 20 parts ether carboxylate
     anionic surfactant 60-486; 1 part NaCMC; 29 parts sodium sulfate (Formu-
     lation Ref. No. 64T1).                                                   *
  Fluorescent whitening agents and minor adjuvants can be added as desired
  without essentially changing the physical character of the product.
  Tendency to cake in storage, as a function of pressure and humidity,
  not investigated.

                                   77

-------
              TABLE 8a.  REPRESENTATIVE LIQUID FORMULATIONS
                         OF SATISFACTORY CHARACTER8
 1.    10.6 parts fatty alcohol ethoxylate nonionic surfactant  68-127;  16 parts
      sodium citrate; 11 parts silicate 0; 10 parts di-sodium  octenyl  succinate;
      water q.s. 100 (Formulation Ref.  No. 7?).
 2.    14 parts ether carboxylate anionic surfactant 40-332;  5.7 parts  silicate
      D; 22 parts SHIM; 10 parts sodium xylene sulfonate  (Formulation  Ref. No.
      71).
 3*    10 parts fatty alcohol ethoxylate nonionic surfactant  68-127; 6.7 parts
      silicate N; 25 parts SHIM; 4.5  parts di-sodium octenyl succinate; vatet
      q.s.  100 (Formulation Ref. No.  59-1).
 4.    12 parts alpha olefin sulfonate anionic surfactant  22-155; 4.8 parts
      silicate D;  18 parts SHIM; 7.7  parts sodium xylene  sulfonate; water
      q.s.  100 (Formulation Ref. No.  65-1).
 5.    12 parts alpha olefin sulfonate anionic surfactant  22-155; 4.8 parts
      silicate D;  18 parts SHIM; 5.6  parts sodium xylene  sulfonate; 8  parts
      isopropanol; water q.s.  100  (Formulation Ref. No. 60-1).
a NaCMC does not dissolve readily in these formulations, but can be suspended
  with or without other anti-redeposition agents and auxiliaries.  About 1
  part NaCMC per 15-20 parts surfactant is a suitable proportion.
                                  78

-------
  Table 9.   STIMULATORY  EFFECT  ON  GROWTH  OF ALGAE
(Positive is stimulating - negative  is  inhibiting.)
                                   SPECIES
Item #
1


2

3
4
5
6
Code //
20-146


22-155


43-83
68-127
68-134
Class of
Compound
Low titer
soap


Alpha
Olefin
Sulfonate

Sodium
tetasilicate
Hydroxylated
Nonionic
Fatty
Alcohol
Ethoxylate
Fatty
Alcohol
Ethoxylate
Anabaena
Slightly
positive at
10 ppm. No
effect at
0.1 and
1 ppm.


"
No effect
at 7 ppm.
Negative at
35 and
70 ppm.
No effect
at 5 ppm.
No effect
at 5 ppm.
Slightly
negative at
1 ppm.
Microcystis
No effect
at 1 and
10 ppm.


No effect
at 1 and
10 ppm.

No effect
at 50 ppm.
No effect
at 1 ppm.
Slightly
negative at
5 ppm.

Selenastrum
 	


No effect
at 1 ppm

No effect
at 1 ppm.
No effect
at 1 ppm.
	

Navicula
No effect
at 0.1, 1,
and 10 ppm.
No effect
at 0.1 and
1 ppm.
Slightly
positive at
10 ppm.

Excess over
amount in
medium has
no effect.
No effect
at 1 ppm.
	
No effect
at 1 ppm.
                     79

-------
Table 9 (Continued)
                                               SPECIES
Item #

7

8
9


10


11


12



13


Code 1

20-138

43-64
54-433


42-348


56-445


40-312



38-279


Class of
Compound

Fatty
Alcohol
Ethoxylate

Commercial
High
Carbonate
Detergent
Zwitter-
ionic
Sulfonate

Zwitter-
ionic
Sulfonate

SHIM
(HEIDA)

SAND



Diglycollic
Acid


Anabaena
No weight
effect,
but cells
altered
at 0.5
and 5 ppm.
No effect
at 5 ppm.
No effect
at 1 and
5 ppm.
Slightly
negative at
1 ppm. No
effect at
0 . 1 ppm.
No effect
at 1 and
5 ppm.

No effect
at 1 and
5 ppm.

-
No effect
at 1 and
5 ppm.

Micro cystis

No effect
at 0.5 and
5 ppm.

Negative
at 5 ppm.
No effect
at 1 and
5 ppm.
Slightly
negative at
1 ppm. No
effect at
0.1 ppm.
No effect
at 1 and
5 ppm.
No effect
at 5 ppm.
Slightly
negative at
1 ppm.
No effect
at 1 ppm.
Slightly
positive at
5 ppm.
Selenastrum

No effect
at 0.5 and
5 ppm.

Slightly
negative
at 5 ppm.
No effect
at 1 and
5 ppm.
Slightly
negative at
1 ppm. No
effect at
0.1 ppm.
No effect
at 1 and
5 ppm.
No effect
at 5 ppm.
Slightly
negative at
1 ppm.

No effect
at 1 and
5 ppm.

Navicula

	

No effect
at 5 ppm.
No. effect
at 1 and
5 ppm.
'
No effect
at; 0.1 and
1 ppm.

No effect
at 1 and
5 ppm.
i
No effect
at 1 and
5 ppm.


NO effect
at 1 and
5 ppm.

                                80

-------
Table 9 (Continued)
                                               SPECIES
Item #

14

15
16


17
18

19
Code #

60-486

90-730
86-700


80-647
20-147

34-249
Class of
Compound
Ether car-
boxy late
anionic
s,ur fact ant

Anionic
sulfonate
surfactant
Standard
phosphate
built
detergent

Monomer ic
builder
CMOS
High titer
soap
IAS
anionic
surfactant
Anabaena
No effect
at 1.0 ppm.
Slightly
negative
at 0.1 ppm.
No effect
at 1.0
and 10.0
ppm.
No effect
at 10.0
and 20.0
ppm.
No effect
at 1.0
ppjn ,
Slightly
negative
at 10.0 .
ppm.
4
No effect
at 1.0 and
10.0 ppm.
Microcystis

No effect
at 1.0
and 5.0 ppm.
No effect
at 1.0 ppm.
Slightly
positive at
10.0 ppm.
Positive
<400%) at
10.0 ppm.
Positive
(2507.) at
20.0 ppm.
No effect
at 1.0 and
10.0 ppm.
No effect
at 1.0 and
10.0 ppm.
No effect
at 1.0 and
10.0 ppm.
Selenastrum

No effect
at 1.0
and 5.0 ppm.
NO effect
at 1.0
ppm.
Slightly
positive
at 10.0 ppm.
Positive
(200%) at
10.0 and
20.0 ppm.
No effect
at 1.0 and
10.0 ppm.
mw 
No effect
at 1.0 ppm.
Very slight-
ly negative
at 10.0 ppm.
Navicula

No effect at
1.0 and 10.0
ppm. Slightly
negative at
0.1 ppm.
No effect at
1.0 ppm.
Very slightly
negative at
10 ppm.
No effect at
10.0 ppm.
Very slightly
positive at
20.0 ppm.
No effect at
1.0 and 10.0
ppm.
'No effect at
1.0 ppm.
Slightly
negative at
10.0 ppm
No effect at
1.0 ppm.
Positive (163%)
at 10.0 ppm.
                                81

-------
                                                       Table 10



                             ACUTE AQUATIC  TOXICITY OF DETERGENTS AND THEIR INGREDIENTS
oo
N>
Item
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Code
20-151
20-152
20-138
43-67
68-127
51-101
51-100
68-134
51-93
43-64
26-189
26-191
43-83
38-279
20-141
42-353
54-433
Description
Glucoheptonic acid
Sodium citrate
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Commercial detergent-high carbonate type
Hydroxylated nonionic surfactant
Hydroxylated nonionic surfactant
Hydroxylated nonionic surfactant
Diglycollic acid builder
Polymeric builder
Sulfo zwitterionic surfactant
Sulfo zwitterionic surfactant
96 hr.
Tim
Fish
ppm.
>2000
1710
2.87
3.45
3.87
3.95
2.73
2.89
3.7
26.7
14.8
196
37
> 490
680
.76
7.7
96 hr.
TLm
Snail
ppm.
>2000
1415
23.1
6.01
6.1
4.03
4.3
3.33
9.5
25.8
>490
89.5
165
>490
420
1.0
6.6
ppm. to
cause
50% redn.
in growth,
7 days
Diatom
>1800
1200
4.5
185
313
900
270
625
123
155
890
125
100
750
62
3.8
35

-------
                                                Table 10  (Continued)
GO
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34

46^356
40-332
48-373
22-155
62-491
18-136
64-^511
40-312
56-445
64-1
64-2
67-1
80-647
90-730
104-860
10JO-823
106-866

Carboxy zwitter ionic surfactant
Ether Carboxy anionic surfactant
Amine oxide surfactant
Alpha olefin sulfonate anionic surfactant
Ether sulfonate anionic surfactant
NTA builder
Formulation of 22-155 and NTA
SAND builder
SHIM builder
Citrate formulation with 60-486 surfactant
Citrate formulation with 54-433 surfactant
Citrate formulation with 42-348 surfactant
CMOS monomer ic builder
D-116 anionic surfactant
FOCNa polymeric builder
Calnox 214 DN polyacrylic builder
Maleic telomer builder
t
10.5
3.15
3.7
4.25
.57
500
10.0
490
> 100
23.7
20.2
44.0
> 560
20.5
> 560
> 560
13.3
4.7
3.8
6.8
.84
500
15.6
490
> 100
24.0
98.1
56.0
> 560
32.3
> 560
> 560
16.4
64.5
6.0
24.2
25
500 
54.9
870
> 100
> 100
21.6
22.1
229% growth
at 100 ppm
17.3
> 560
300% growth
                                                                         > 560
                                                                        > 560
                                                                                                             (a)
at 100 ppm

890% growth
at 100 ppm
                                                                                                             (a)
      (a)
These figures indicate  stimulation of growth.

-------
                               Table  11

                  ESTIMATION OF BIODEGRADABILITY OF
               MATERIALS USED  IN DETERGENT FORMULATIONS
I.   Materials considered biodegradable
     V.
          Code No.            Type

          43-83               Hydroxylated nonionic surfactant
          40-332              Ether carboxylate anionic surfactant
          42-348              Sulfo zwitterionic surfactant
          38-279              Diglycollic acid builder
          66-541              Monomeric builder
          74-606              Monomeric builder, Mellitic acid
          56-445              SHIM builder
          80-647              Monomeric builder, CMOS
          60-486              Ether carboxylate surfactant
          20-145              Sugar ester surfactant
          90-730              Anionic sulfonate surfactant
         104-860              Polymeric builder, hydroxylated acrylic


II.  Materials considered non-biodegradable

          Code No.            Type

          76-620              Monomeric builder
          43-65               Polymeric builder
          66-530              Polymeric carbohydrate type builder
          74-602              Polymeric carbohydrate type builder
          58-466              Polymeric builder
          86-709              Polymeric builder, maleic copolymer
          40-310              Polymeric builder, maleic copolymer
          92-745              Polymeric builder, acrylic
          43-74               Polymeric builder, acrylic
          98-806              Polymeric builder
          98-807               Polymeric builder
         100-824               Polymeric builder, acrylic
         100-822               Polymeric builder, carbohydrate
         106-871               Polymeric builder, maleic
         102-833               Monomeric builder
                                   84

-------
                         Table 11 (Continued)



III.   Materials of questionable (slow or incomplete)  biodegradability

          Code No.            Type

          100-821             Polymeric builder
          100-823             Polymeric builder,  acrylic
          102-834             Polymeric builder,  carbohydrate
          106-866             Polymeric builder,  maleic telomer
                                    85

-------
                                                       Table 12
                                     HAZARD TEST RESULTS.  DETERGENT FORMULATIONS
oo
Ident. No.
64-2
65-1
65-2
64-1
67-1
56-445
43-64
LP-23
LP-24
LP-25
LD50 ORAL
mg/kg
> 5
< 5
> 10
> 10
4.13 (m)
3.55 (f)
2.61 (m)
3.83 (f)
	
> 5
> 5
> 5
LD50 DERMAL Rabbit skin Rabbit eye
rag/kg irrit .score irr it . W
^ n n (-  imt 
> *'** (39,25,21)
> 2 > 5.5 irrit.
(27,27,22)
0.99(a* 4.0 irrit.
(32,26,19)
> 2 2.9 irrit.
(35,27,22)
> 1, < 2(a) 	 irrit.
(50,47,38)
o 91(a)
j.zi  -- -
	 	 	
> 2 0.38 	
> 2 	 	
> 2 	 	
Esophageal
irrit.
equal to
sucrose control

	
equal to
sucrose control
equal to
sucrose control
	
very slight
positive
	
	

     (a)  Wide variation;  severe renal damage.
     (b)  Figures  are eye  scores at 24, 48 and 72 hours.
     (c)  Five week repeated insult patch test on 53 panelists,
                                                                                         Human patch test
                                                                                             negative
                                                                                                         (c)
                                                                                             negative
                                                                                             negative

-------
                              Table 12a
              IDENTIFICATION OF FORMUIATIONS IN Table 12

Ident No.                           Composition
64-2           20/20/1/30/29.  Surfactant 54-433,  Builder citrate, Solid.
65-1           12/4.8/0/18/7.7/qs H.O.  Surfactant 22-155, Builder SHIM,
               Hydrotrope Na xylene sulfonate,  Liquid.
65-2           10/6,7/0/25/4.5/qs H20.  Surfactant 68-127, Builder SHIM,
               Hydrotrope Na octenyl succinate, Liquid.
64-1           20/20/1/30/29.  Surfactant 60-486,  Builder citrate, Solid.
67-1           20/20/1/30/29.  Surfactant 42-348,  Builder citrate, Solid.
56-445         SHIM (HEIDA) builder, 257. aqueous solution.
43-64          Commercial phosphate-free, high carbonate detergent.
LP-23          Sodium xylene sulfodate, 20% aqueous solution.
LP-24          Sodium octenyl succinate, 5% aqueous solution.
LP-25          Sodium nitrilotriacetate (NTA),  25% aqueous solution.
                                    87

-------
                                                   Table 13

                        EFFECT OF MULTIPLE WASHINGS ON BUILD UP OF IMPURITIES  IN FABRIC
00
00
                                                 Alcohol Extractable*
                                                 Content of Fabric,  %
Ash Content*
of Fabric, %
Ident .
Number
86-700
88-722
88-726
86-706
86-707
86-708
20-147
MM
Detergent
Type
AATCCWOB
'Commercial high carbonate
Commercial high silicate
Soap & lime soap disperser
Soap & lime soap disperser
Soap & lime soap disperser
Soap & silicate 85/15/0/0/0
None-Hard Water Alone
After
20 Washings
Blend
Fabric
.30
--

.74
1.43
1.14
2.09
.58
Cotton
.77
 

1.49
2.41
1.47
3.31
.58
After
50 Washings
Blend
Fabric
.64
.54
.61
2.39
2.20

3.50
.78
Cotton
.36
.40
.50
2.33
2.12

5.71
.61
After
20 Washings
Blend
Fabric
.29
--
--
.37
.39
.39
.50
.28
Cotton
.09


.13
.24
.19
.60
.03
After
50 Washings
Blend
Fabric
.36
7.5
.80
.56
--
.54
.77
.31
Cotton
.08
10.6
.41
.39
--

1.19
.08
        Original unwashed blend fabric averaged .81% alcohol extractable and .33% ash.
        Original unwashed cotton fabric averaged .47% alcohol extractable and .05% ash.

-------
        '  I
                                AA' CCWOB
         Sbaa-lsiliciktei
            .1
.2
.3
.4
     Detergent concentration in bath  (%)
Figure 1.   Detergency v. concentration.  Item 20-147 high titer
           soap.  Series ref.  210.  Empa soil.  200 ppm water.
                 89

-------
 0)
 c
 0)
 (V
 O)
 c
U
          Detergent concentration  in  bath  (%)


     Figure  2.   Detergency v. concentration.  Item 86-706.
                Soap-lime soap disperser.  Series ref.  210,
                Empa soil.  200 ppm water.
                    90

-------
     Detergent concentration in bath  (%)


Figure 3.   Detergency v. concentration.  Item 86-707.
           Soap-lime soap disperser.   Series ref. 210,
           Empa soil.  200 ppm water.

               91

-------
     Detergent concentration In bath
Figure 4.   Detargeney v. conctntratlon,  Item 86-708.
           Soap- lima soap dliparaer.  Series  raf.  210.
           Empa  loll.  200 ppm water.

                 92

-------
               Detergent concentration  in  bath (%)

Figure  5,  Detergancy v.  concentration.  Item 90-730  anlonlc
          ulfcmate.  Serlea  ref, 243.  Colgate soil.  Tup
          water.  Blend  fabric.
                          93

-------
                Detergent concentration in bath  (%)
Figure 6.   Detergency v. concentration.   Item 90-730 anionic
           sulfonate.  Series ref. 243.   Colgate soil.  Tap
           water.  Cotton.

                          94

-------
                                                                     .3
               Detergent concentration  in  bath  (%)

Figure 7-   Detergency v. concentration.  IAS  and  Item 90-730
           anionic  sulfonate.  Series ref.  239C.  Colgate soil.
           200  ppm  water.  Blend fabric.
                           95

-------
V)
Cfl
0>
c
0>
0>
O)
c
CO
                      Detergent  concentration in bath (%)
     Figure 8.  Detergency v. concentration.  IAS and Item 90-730
                anionic sulfonate.  Series ref. 239C.  Colgate  soil.
                200 ppm water.  Cotton.
                              96

-------
Q>


I
a
tn
(0
O

o>
                      Detergent  concentration in bath  (%)


      Figure 9.  Detergency v. concentration.  IAS and  Item 90-730

                 anionic sulfonate.  Series ref.  239.   Spangler  soil

                 multicycle.  200 ppm water.  Blend fabric.
                                  97

-------
 o
 >>
 u
o

0)
in
o>
                                              U4-J.Q JJA6
      Figure 10.
    Detergent concentration in bath (%)



Detergency v.  concentration.  IAS and Item 90-730

anionic sulfonate.   Series ref. 239.  Spangler soil

multicycle.   200 ppm water.  Cotton.
                                  98

-------
Figure 11.
    Detergent  concentration in bath (%)

Detergency v. concentration.  IAS and LAS-CMOS (item 80-647)
and Item 90-730 anionic sulfonate.   Series ref.  243.
Spangler soil multicycle.  Tap water.  Blend  fabric.

               99

-------

u
u
o
o
o


tf)
                                                         (20/8/1X30/41)
                      Detergent concentration  in  bath  (%)

     Figure 12.  Detergency v. concentration.  IAS  and IAS-CMOS (item 80-647)
                 and Item 90-730 anionic sulfooate.  Series ref. 243.
                 Spangler soil multicycle.  Tap  water.  Cotton.
                                100

-------
10
(A
0
C
0

at
c

a
     Figure 13.
     Detergent concentration in bath (%)

Detergency v.  concentration.  Items 42-350 and 42-353
zwitterionic.   Series  ref. 247 and 252 (for AATCCWOB)
Colgate soil.   200 ppm water.  Blend fabric.
                                  101

-------
Figure 14.
     Detergent concentration in  bath (%)

Detergency v.  concentration.  Items 42-350 and 42-353
zwitterionic.   Series ref. 247 and 252 (for AATCCWOB).
Colgate soil.   200  ppra water.  Cotton.

                102

-------
                Detergent concentration in bath  (%)

Figure 15.   Detergency v.  concentration.  Items  104-856 and  108-880
            anionics.  Series refs. 252 (AATCCWOB)  250 and 256.
            Colgate  soil.  200 ppm water.   Blend fabric.

                            103

-------
Crt
CO
0)
c
 c

 0)
.c
O
                                                                            .3
     Figure 16.
    Detergent  concentration in bath (%)


Detergency v. concentration.   Items  104-856 and 108-880
anionics.  Series refs.  252  (AATCCWOB) 250 and 256.
Colgate soil.  200 ppm water.  Cotton.

                104

-------
                  Detergent  concentration in bath  (%)

Figure 17.   Detergency v.  concentration.  Items 104-855 (detergent D)  and
            96-782 (detergent E).  Series refs. 252 (AATCCWOB)  and 248.
            Colgate soil.   200 ppm water.  Blend fabric.

                            105

-------
c
a;
 0)
 a>
 c
(J
                                                      AATdCWftE
                                                            i       I
                                         I-

                            .1
                                     .2
.3
   Figure 18.
      Detergent  concentration in bath (%)



Detergency v. concentration.   Items 104-855 (detergent D)

and 96-782 (detergent  E).  Series refs. 252 (AATCCWOB)  and  248.

Colgate  soil.  200 ppm water.  Cotton.


                 106

-------
0)
73



1
IE
4)
 (B

 (0
 (0
 0)

                      Detergent concentration  in  bath  (%)


    Figure 19.   Detergency v.  concentration.  Items 104-855 (detergent D)
                and 96-782 (detergent E).  Series refs. 253 and 254.   Spangler
                multicycle.  200  ppm water.  Blend fabric.

                                  107

-------
o
TO
o
0)
0)
c
Figure 20.
                      Detergent concentration in bath  (%)

               Detergency v. concentration.  Items 104-855  (detergent D)
               and 96-782 (detergent E).   Series refs.  253  and 254.  Spangler
               multicycle.  200 ppm water.  Cotton.

                                 108

-------
                                                   AATCCWOB

                                                *   Detergent C

                                                O   Detergent T
                        .1                     -2
                  Detergent  concentration in bath (%)
                                                          .3
Figure 21.
Detergency v. concentration.  Items 96-783 (detergent C)  and
96-784 (detergent T).   Series ref.  240.  Colgate soil.  200 ppm
Blend fabric.
                   109

-------
 30
      Cotton
                                                   AATCCWOB

                                                 *  Detergent C

                                                 O  Detergent T
                        .1                      .2

                  Detergent  concentration  in bath (%)

Figure 22.  Detergency v.  concentration.   Items 96-783 (detergent C) and
           96-784 (detergent T).  Series  ref. 240.  Colgate  soil.
           200 ppm water.  Cotton.

                               110
.3

-------
                  Detergent  concentration in bath (%)

Figure 23.   Detergency v. concentration.   Series ref. 259 (AATCCWOB)
            268  (HEIDA).  Colgate soil.   200 ppm water.  Blend fabric.
                             Ill

-------
 (A
 C/>
 Q>
 c



 c


U
                     Detergent concentration in  bath (%)
   Figure 24.  Detergency v.  concentration.  Series ref.  259  (AATCCWOB)

               268 (HEIDA).   Colgate soil.  200 ppm water.  Cotton.

                                112

-------
                  Detergent concentration in bath (%)

Figure 25.   Detergency v.  concentration.  Item 100-823.   Series ref. 252
            (AATCCWOB) 255 (item 100-823).  Colgate soil.   200 ppm water,
            Blend fabric.
                             113

-------
0>
C
 0)
 O)
 C
O
   Figure  26.
       Detergent concentration in bath (%)


Detergency v.  concentration.  Item  100-823.  Series ref.  252
(AATCCWOB) 255 (item 100-823).  Colgate soil.  200 ppm water,
Cotton.
                                114

-------
(A
tf)
0)
C
9
C
u
                      Detergent concentration  in bath (%)

   Figure 27.   Detergency v.  concentration.  Item 104-860.   Series  ref.  259
       .',     -  (AATCCWOB)  257 (item 104-860).  Colgate soil.   200 ppm water.
               Blend  fabric.
                               115

-------
(A
to
Q>
'C
0)
0)
O)
C
                     Detergent  concentration in bath  (%)


   Figure 28.   Detergency v. concentration.  Item 104-860.   Series ref. 259
                (AATCCWOB) 257 (item 104-860).  Colgate soil.   200 ppm water.
                Cotton.

                                 116

-------
0>
c
JC
$
C
(0
                      Detergent concentration in bath (%)


   Figure 29.  Detergency v. concentration.  Item  106-866.  Series refs. 258,

               259,  260.  Colgate soil.  200 ppm water.   Blend fabric.

                                 117

-------
(A
0)
C
0>
0)
O)
  Figure 30.
      Detergent concentration in bath (%)


Detergency v.  concentration.  Item 106-866.  Refs.  258,  259, 260,
Colgate soil.   200  ppm water.  Cotton.

                 118

-------
0>
"o
o
0)
 8
 
-------
o
o
o
0>
CO
(0
0>

0)
   Figure 32.
      Detergent concentration  in  bath (%)


Detergency v.  concentration.  Item 106-866.   Series ref. 267
Spangler multicycle.  200 ppm water.  Cotton.
                                120

-------
                                                   AATCCWOB
                 Detergent concentration in bath  (%)

Figure  33.  Detergency v. concentration.  Item 80-647.  Series ref. 243.
           Colgate soil.  200 pptn water.  Blend fabric.

                          121

-------
                  Detergent concentration  in  bath (%)

Figure 34.   Detergency v. concentration.  Item 80-647.  Series ref.  243.
            Colgate  soil.  200 ppm water.   Cotton.
                            122

-------
Figure 35.
      Detergent concentration  in bath (%)

Detergency v.  concentration.  Item 90-279.  Series ref. 240.
Colgate soil.   200 ppm water.  Blend  fabric.

                 123

-------
                                                                        .3
Figure 36.
       Detergent  concentration in bath (%)
Detergency v.  concentration.'  Item 90-279.   Series ref. 240.
Colgate soil.   200 ppm.  Cotton.

                124

-------
                          APPENDIX A*

                  TEST METHODS, NON-LAUNDERING


I.    BIODEGRADABILITY

A.    Aerobic Biodegradability Tests

     1.   Affirm that the "active" organic surfactant is degraded aero-

          bica*ily under conditions of the Bunch-Chambers test procedure
          r
          LR- L- Bunch and C. W.  Chambers, J.  Water Pollution Control

          Fed., 39 (2), 181 (1967)].

     2.   Test whether the proposed builder candidate (if it is organic)

          undergoes degradation in this static aerobic procedure.

          a.   If the builder is not degraded,  re-test the organic
               active in the presence of builder.

          b.   If the builder does undergo aerobic biodegradation,
               re-determine the extent of degradation in the pre-
               sence of the surfactant.

     3.   Test biodegradability of organic detergent formulation com-

          ponents other than the active surfactant and builder.

          a.   Retest in presence of surfactant and builder to ascer-
               tain that there is no interference in degradation of
               any component.  This is the test of the final formula-
               tion.

B.   Biostimulation by Biodegradation Products

Test whether algal growth is stimulated  (or inhibited) by the degrada-

tion products  from A.3.a., above.

C.   Toxicity of Biodegradation Products

Test the toxicity of  the biodegradation products  from full detergent
formulations .(A. 3. a.).
     For purposes  of record  the  text of  this appendix is reproduced
     verbatim  from material  in the  contract proposal and specifica-
     tion.  The protocols  proposed  and described herein are the ones
     subsequently  used  in  performing the contract.

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 D.   Anaerobic Biodegradability Tests
 Test the complete detergent formulations as in A.3.a. except under
 anaerobic atmosphere in the culture flasks.
 In the biodegradability tests, A above, settled sewage (from the
 Washington, D.C. area) or other inoculum specified by the Government
 will be used to inoculate solutions of test materials in BOD water
 containing yeast extract.  The basal medium comprising BOD water (pre-
 pared according to "Standard Methods for Examination of Water and Waste
 Water", 12th ed. Amer. Pub. Health Assoc., New York, 1965) and yeast
 extract will be prepared beforehand and sterilized at 121C for 15 min-
 utes in an autoclave.  The concentration and yeast will be selected
 consistent with the stimulation of microbial growth, but with minimal
 oxygen depletion; for most tests,  yeast concentrations of 20 mg/1 to
 200 mg/1 are satisfactory.  The concentration of test material will be
 at least 20 mg/1 in screening tests.  Our standard for biodegradation
 of LAS type active will be dodecene-1 derived LAS and it must show
 97.5% degradation (as determined by the methylene blue analytical
 method)  in order for us to consider the results valid.  Surfactants
 that  are not methylene blue responsive will be analyzed by suitable
 chemical procedures  when such are  available.  Measurements of foaming
 and/or  surface  tension will be used as auxiliary indications of sur-
 factant  content.
 It  is anticipated  that  analytical  methods  in the parts-per-million
 and parts-per-billion range will be lacking for some components.   In
                                                              k
 such cases the primary  test for biodegradability will be a standard
 BOD test.  For this we  use  the method  given in "Standard Methods  for
 the Examination of Water and Waste Water",  American Public Health
Association, Inc. 12th  ed.  (1965)  p. 415ff.   This is modified to  the
extent that the dissolved oxygen (DO)  is measured by the method
                               126

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and kit equipment described in Catalog #10,  second revised edition
of Hach Chemical Company, Ames, Iowa, p. 47ff.   The BOD value, suitably
corrected, is an index of the biodegradability of the substrate.

II.  ALGAL STIMULATION
The basic test for algal stimulation used in this program was the Pro-
visional Algal Assay Procedure ("PAAP test") issued by the Joint Indus-
try-Government Task Force on Eutrophication, February, 1969, and its
subsequently issued revisions.  The test was made on four different
organisms.  Details are as follows:
A.   Organisms Used:
     Selenastrum capricornutum (green)
     Microcystis aeruginosa (blue green)
     Anabaena flos-aquae (blue green)
     Navicula seminulum  (diatom)
B.   Phyaica1 Arrangement s
Temperature - All algal work is carried out in a constant temperature
room maintained at 24C   0.5C.  Ambient temperature is recorded con-
tinuously and 7-day chart records are kept.
Lighting and shaking rates - All cultures are illuminated with cool-
white fluorescent lamps.  Light levels are checked weekly with a
Cossen Tri-Lux foot-candle meter.  Navicula and Selenastrum are grown
on a laboratory-constructed shaker with a plexiglas platform, with
the lights placed underneath this platform i.e. with "bottom-illumina-
tion" at 200 foot candles.  For Microcystis and Anabaena a commercial
(Eberbach Corporation) reciprocal shaker is used with overhead illumi-
nation at 150 foot candles.  Both shakers are operated at 100 strokes/
minute with a 2 inch throw.
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 C .    Media for Carrying  Stock Cultures
 Three different stock culture media  are used.  All media are prepared
 with glass-distilled water.   Selenastrum  capricornutum and Anabaena
 f los -aquae are maintained on the  medium of  the published PAAP procedure,
 Microcystis aeruginosa does  not grow well in the PAAP medium, and
 stock cultures are maintained in  a solution described by Hughes, Gor-
 ham and Zehnder*.   The major nutrients can  be prepared as individual
 stock solutions,  1000X the final  concentrations needed, so that 1.0 ml
 of  each is used for each liter of medium.  The final concentrations of
 major nutrients,  in grams per liter  of medium, are as follows:  NaNO_,
 0.496;  I^HPO,, 0.039; MgS04=7H20, 0.075;  CaCl^-Zfiy), 0.036; Na CO.,
 0.020;  Na SiCy9H20, 0.058;  ferric citrate, 0.006; citric acid, 0.006;
 EDTA,  0.001.   The  final  medium also  contains 0.10 ml/liter of a "micro-
 nutrient" solution containing the following salt mixture  (in grams/
 liter):   H3B03,  3.100; MnS04'4H20, 2.230; ZnSO^H^O, 0.287;
 Mo7024-4H20,  0.088;  CoCNO^-ei^O,  0.146;  Na^O^E^O,  0.033; KBr,
0.119; KI,  0.083;  Cd^O^^O,  0.154;  NiSO^NH^SO^ei^O,  0.198;
VOS04-2H20, 0.020;  and Al^SO^^SO^ 241^0,  0.474.  Although,  in
the original publication,  autoclaving of this medium is  recommended
it was found that  a precipitate  is  formed when  this  medium is auto-
claved.  The procedure has therefore been changed, and the medium is
filter- sterilized  (0.45 micron millipore filter),  leaving out the
ferric citrate and  the "micronutrients"  which are  then added  to. the
filtered medium.   (Iron salts, and  other heavy  metal salts, tend to
precipitate out on Millipore filters).   The final pH of  this medium, is
9.5.
*E. 0. Hughes, P. R. Gorham, and A. Zehnder,  "Toxicity of  a Unialgal
 Culture of Microcystis Aeruginosa" Can. J. Microbiol. 4,  225-236
 (1958).
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Navlcula seminulum is maintained in the "soft water" medium described
in ASTM procedure D-2037-64T, "Evaluating Inhibitory Toxicity of In-
dustrial Waste Waters."  The final medium contains the following salts
(in grams per liter):  Ca(N03)2'4H20,  0.0761; K2HPO,, 0.0080;
0.0400; KC1, 0.0200; Na2Si03'9H20, 0.3540; CaCOg,  0.0100;  and
0.0400.  It also contains 4 ml/liter of soil extract (prepared by ex-
tracting 35g of "enriched garden soil" (commercial African Violet Soil)
with 350g of boiling water and filtering through ashless filter paper).
It also contains 1.0 ml/liter ferric citrate solution (1.820g ferric
citrate plus 1.30g citric acid per liter); and 1.0 ml/liter of micro-
metabolite solution (this contains the following salts,  in mg/liter:
ZnS04, 20; MnS04, 14; AlCl^ei^O, 36;  HgBO^ 20; LiCl, 10; and
CoCl26H20, 10).  The major nutrients are prepared as concentrated
individual stock solutions.  The micrometabolite solution is pre-mixed.
The pH of the medium, before sterilization, ranges from 9.8 to 10.5,
and is adjusted to pH 9.5 with HC1.  The final solution is sterilized
by autoclaving at 20 psi for 20 minutes.

D.   Experimental (Teat) Media
For Anabaena, test media and stock culture media are identical; for
Selenastrum the test media are half the concentration of the stock
media.  In each case, after addition of the test material (but before
addition of culture inocula) the pH is readjusted to 7.5 by the addi-
tion of either IN NaOH or IN HC1  (usually, one or two drops per liter
of medium).
The test medium for Micorcystis  is also the  standard PAAP medium.
However, before use, Microcystis maintained  in the "rich" stock
medium is subcultured twice, for  7 days each time, in the PAAF medium.
This is necessary to reduce the effects of nutrient  carry-over.
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 The ASTM medium used for Navicula stock cultures was designed for
 toxicity testing rather than for evaluating biostimulatory potential
 of materials, and is a "rich" medium.  Therefore it must be diluted
 if the addition of biostimulatory materials is to show any effect.
 The test medium used at present contains one-fourth (1/4)  the concen-
 tration of all constitutents of the stock medium, except for sodium
 metasilicate; the silicate concentration is kept at the original level.
 The pH of this medium is adjusted to 9.5.
 Before inoculation into test media, cells are centrifuged and washed,
 essentially as described in the PAAP protocols,  except that they are
 washed with test medium rather than with distilled water.   The volume
 of inoculum (except for Anabaena) is adjusted so that, at the start
 of the experiment,  cell concentrations will be as  follows:   Selenastrum.
       344
 1  x 10 /ml;  Microcystis, 5 x 10 /ml; and Navicula, 4 x 10 /ml.
 Anabaena,  a chain forming organism, is  not counted.  A uniform suspen-
 sion is prepared (30 seconds in sterile Waring Blender)  and aliquots
 are dispensed into  test flasks.  A larger aliquot is filtered through
 a  0.45n millipore filter and dried for  determination of biomass.
 (When  100 ml of 7-day stock culture are centrifuged,  and the pellet
 resuspended  in 100  ml of medium,  50 ml  of suspension yield approxi-
mately 5 mg  of dried material.)   Generally,  2.0  ml aliquots are used,
                                          _3
 leading to a "dry weight" level of 2 x  10   rag/ml.
For any of the organisms the concentration of test material added to
the test medium can vary widely,  and the choice  of a concentration
level  should be  guided  by the expected  action of the test  material and
by its  expected  concentration in  the field.   It  can advantageously
be set  between .1 and  10.0  ppm  (mg/liter)  in most cases.
                               130

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E.    Methods for Evaluating Growth
Three different methods for evaluating algal growth are used:  (a)
direct cell count, (b) absorbance at 450 and 600 am;  and (c)  biomass
(dry weight).
The last method, gravimetric determination of dry weight,  is  used
only with Anabaena.   Matched weight, 47 mm 0.45|i Millipore filters
ace used in a "double" assembly; that is, both filters of the matched
pair are placed in the filter holder, and the entire culture filtered.
Each filter is dried under identical conditions and weighed;  the dif-
ference in weight between the two filters is taken as the dry weight
of Anabaena in the volume filtered.  During this "screening" stage
7-day cultures of Anabaena are harvested and weighed, thus, this is a
single-point estimation of total growth, not an estimation of rate.
Navicula growth also is estimated by total growth during a fixed time
period (10 days or more) rather than by rate.  Since Navicula tends
to stick to the walls of the flasks, and to form gelatinous masses,
all flasks are carefully scraped and the contents mixed rapidly in
a Waring Blender  (as recommended in the ASTM procedure).
Growth of both Selenastrum and Microcystis is estimated both by total
growth, and by growth rate.  Since  these algae are unicellular and do
not tend to clump or adhere  to vessel walls, small aliquots  can be
removed periodically throughout the time of incubation, and  increases
in cell numbers can be followed readily.  These  two  organisms are
grown in 300 ml Nephelo flasks  (Bellco  Glass,  Incorporated,  Vineland,
New Jersey, Catalog No. 524) so that absorbance  of the  culture can
be measured with  a B&L Spectronic  20 directly  in the flask,  without
removal of aliquots.   For  each  experiment,  5 control flasks  and 5
flasks supplemented with test compound  are  used.
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 A Coulter Counter, Model Z I, equipped with a Mean Cell Volume/Hema-
                           a
 tocrit attachment is used for cell counts and determination of mean
 cell volumes.  The same 70^ aperture can be used for each of the or-
 ganisms counted.  Isoton, a commercially available electrolyte solu-
 tion, is used as the diluent.

;III. AQUATIC TOXICITY
 Two types of test were used in the program, referred to for brevity
 as the acute or screening test and chronic test.  The chronic test re-
 quiring a minimum of two months for fish and varying times for other
 organisms, was ultimately used on only two formulations.  The screen-
 ing "-test involves a 96 hour exposure,  and was used,  as its name implies,
 to screen out candidate materials that are definitely unsatisfactory
with regard to aquatic toxicity.   Three test organisms are used in our
present screening procedure:   a fish,  a gilled snail, and a diatom.
In the chronic tests  it is planned to  use the following organisms:
      1.    Two diatoms (algae)--desirable food species, one typical
           of lakes,  the other typical  of streams.
      2.    Insectsa  genus and,  if possible,  a species typical of as
           many types  of streams  as possible.
    
      3.    Two snailsa genus,  and,  if possible,  species typical of
           many types  of lakes  and streams as  possible; a pulmonate
           and a gill  breather.
     4.    Crustaceaa  genus and  species typically found in lakes.
     5.    Fish--catfish or suckers,  algae and detritus feeders.
     6.    Fish--sunfish species found  in many types  of lakes  and
           streams.
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A.    Gene ra1 Acute Test ing Procedures
The following general considerations apply to acute testing procedures:
     1.   All acute bioassays will be conducted using continuous flow
rather than static techniques.  The continuous flow method insures
that waste products of metabolism do not build up in the test container,
decrease the chances of test material adhering to the sides of the
container, allow minimum -nodification of the environment by the test
organism, eliminates the need for any aeration in the test chamber
since aerated dilution water is constantly flowing, and insures ac-
curate monitoring of test concentrations throughout the test period.
All these factors, if not controlled, result in inaccurate and un-
reliable test results.
     2.   All acute bioassay tests will be conducted over a 96-hour
test period with mortality readings taken every 24 hours.  The 96-hour
exposure period is now the accepted acute exposure time by most au-
thorities .  Shorter exposure times very often produce a distorted
picture because of possible  lag of toxic effect.
     3.   A minimum of five  concentrations plus control will be used
for each test material.  The concentrations will be set up in a
logarithmic series as outlined in Standard Methods.  This  logarithmic
series has proved to be most  efficient  over the years in determining
critical  toxic concentrations.  Partial mortality  of the test organ-
isms must be obtained at each of  two  concentrations, three if possible,
for each  test period.
     4.   General observations concerning behavior will be made.
These  include increase or  lack of movement,  erratic movement,  loss  of
equilibrium  (partial or complete),  and  any  uncommon reaction to  the
 test chemical.
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       5.    Simple  graphic  interpolations of dose effect will be made
  in order  to  derive  a  96-hour TLm  (medium tolerance limit) and in
  addition  Lichfield  and Wilcoxon's probit analysis method will be
  employed  to  derive  the LC, LC_0, and LC   and their confidence
  limits for each 24-hour test period.
       6.    All tests will  be conducted in one dilution water, a soft
  water and  at one  temperature.
       This  method  gives the ED5Q, slope of the curve and their confi-
  dence limits.  It uses original data throughout and uses 0 and 100 per-
  cent  effects.  The method recognizes heterogeneity when present and
  gives corrected confidence limits in such cases and facilitates the
  comparison of two curves for parallelism and computation of relative
 potency with its confidence limits.  The method is rapid and is used
 without logarithms.   Logarithmic-probability paper is used to plot
 data in original units (i.e.,  percentages and arithmetic values)
 equivalent to the use of logarithms and probits.   Nomographs are used
 to allow a simple arithmetic solution of a dose effect curve which is
 equivalent to the solution by use of logarithms and probits.  This
 method is  recommended by Pesticides Regulation Division Animal Biology
 Section U.S.D.A.  and we  have found it to be very effective.
 Specific Bioassay Test Techniques  (fish and snail)
      1.    The fish bioassay experimental technique  will consist of a
 pump-fed system which  meters calculated amounts of  test sample and
 aerated dilution water separately  into  a head jar where they are
mechanically  mixed by  magnetic  stirrer.  The  mixed  concentration of
sample in dilution water then flows  a a fixed rate  into the  bottom
of a five-gallon wide  mouth glass  test  container holding ten test
fish.  The  used mixture of test sample  in dilution  water overflows
the top of  the test jar at the same  rate that the new mixture enters
the bottom  of the test jar.  The rate of flow is one gallon  per hour

                               134

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which past experience has shown is sufficient to maintain physio-
logical dissolved oxygens and C02 levels.   Twenty fish are exposed to
each concentration in the test series,  ten for each of two bioassay
test systems, 0.5 to 1.0 grams fish per liter of test water.  Test
fish will be obtained from a hatchery,  transported to the test site
in water comparable in temperature and quality to that used in the
hatchery and will be acclimated in the laboratory for at least two
weeks at the test temperature before use in the bioassay tests.  Test
fish will receive no food for 36 hours prior to a test or during the
test period to mini-size waste production during the exposure period.
     3.   Snail bioassay experimental techniques will consist of the
same system as outlined above for the fish bioassay except that the
test containers will be 32 ounce glass jars with lids.  Used test
water will overflow through a screened hole in the lid so that no
air space exists in the test jar which would allow the test snails
to remove themselves from the test solutions.  Test snails will be
obtained from local waters.  They will be acclimated in the labora-
tory in the same manner as the test fish.
Specific Bioassav Test Technique (Diatom)
The method used is ASTM D2037-64T "Tentative method of test for evalua-
ting inhibitory toxicity of industrial waste waters".  This refers to
diatoms as part of the fish-food chain.  Although it somewhat resembles
the FAAF test for biostimulation, both test programs are considered
necessary.

B.   Detailed Acute Testing Procedures (account of an actual test)
     1.   Fish
          The Test Organism - The bluegill sunfish, Lepomis macro-
chirus Raf., which has a wide distribution, was used for test purposes.
                               135

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      The fish used in the tests were between 4 and 6 cin in length
 measured from the anterior tip of the head to the end of the caudal
 fin, or tail.  In no individual test did the length of the largest
 specimen exceed the length of the smallest by more than 50 percent.
 The fish were acclimated in the laboratory for a period of two weeks
 at the test temperature of 18C.  Test organisms received no food for
 36 hours before a test or during the test period.  Each fish was used
 for only one test; only healthy fish were used.  Stock cultures which
 had more than 5 percent mortality during the period of acclimatiza-
 tion were discarded.

      Apparatus - The  continuous flow experimental technique consisted
 of a pump-fed system  which metered calculated amounts of sample and
 dilution water separately into a head jar where they were mixed.
 The mixed concentration of sample in dilution water then flowed at
 a  fixed rate into the bottom of a 15 gallon glass stainless steel
 framed  aquarium in which were placed 20 test fish.   The used dilution
 water overflowed the  top of the aquarium at about the same rate that
 new dilution water entered the bottom of the aquarium.   The rate of
 flow was  one gallon per hour.   This was allowed to proceed for 96 hours
 for each  experimental  concentration.
     In all  tests  constant  dilution waters were prepared from distilled
water and A.C.S. grade  chemicals.   Each chemical was pipetted sepa-
rately  from  a concentrated  (200X)  stock solution directly into dis-
tilled water in order to prevent  the  precipitation of chemicals.
Carbon dioxide was bubbled  through the  dilution water to get all the
chemicals into solution.  The  dilution  water was then aerated until
the saturation point of  oxygen was  reached and the  CO-  brought to
the normal level.  Dissolved oxygen was  determined  by the oxygen
                               136

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meter before the fish were introduced and every hour for six hours
thereafter.  At least Eour D.O. readings were made during each
24-hour test period.
Conditions of the Tests
          Constant Temperature:
          Dissolved Oxygen:
          Dilution Waters:
18C
5 to 9 ppm
A prepared water similar in
chemical characteristics to a
soft water referred to as modi-
fied CHU 14.
          KC1
          NaHC03
          MgS04 '
          CaCO
          Ferric nitrate
gms/liter
  0.02
  0.02
  0.04
  0.04
  0.04
  0.01
  0.002
  0.0018
     The dilution water was made u? from distilled water to the quality
 indicated above.

 Addition of Test Organisms
     Twenty fish, 4 to 6  cm long, were added to the mixed solution
 after the dissolved oxygen had been raised to the required level.
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 Control
      A control tank was maintained with each experiment.  In each con-
 trol tank 100 percent survival was required.

 Calculation of the Biologically Safe Concentration
 Application factors for calculation of Biologically Safe Concentrations
 are presently being discussed and several recommendations for these
 factors are available.  Perhaps one of the most recent and authorita-
 tive recommendations coaies from the Report of the Committe on Water
 Quality Criteria, FWPCA, U. S. Department of Interior, 1968.  From
 the section on "Water Criteria for Fish and Other Aquatic Life" the
 proposal Is made that "Concentrations bf materials with non-cumulative
 toxic effects should not exceed 1/10 of the 96-hour TLm value at any
 time or place.  The 24-hour average of the concentration should not
 exceed 1/20 of the Tim value."
 The above recommendation is probably the most widely accepted applica-
 tion factor by state and federal agencies at this time.

      2.    Snail
           The Test Organism - Amnicola limosa (Say.)>  a gilled snail,
was  chosen for test purposes.  The snails used were adults averaging
3 mm in diameter.   They were collected from the Brandywine Creek,
East Branch,  outside of West Chester,  Pennsylvania.

           The  snails  were  acclimated in the laboratory for a period
of four weeks  to  the  dilution water.   Test organisms received no food
for  36 hours before a test or during a test period.  Each snail was
used  for only  one  test  and only healthy snails were used for test
purposes.
                               138

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     Apparatus - Containers for snail tests  were  1500 ml  jars.   Each
jar was fitted with a plastic lid and the  lids  were  perforated  to
allow for gas exchange.  Calculated amounts  of  test  samples  and dilu-
tion water were pumped in two separate streams  to a  head  jar where
they were mixed and the mixture then flowed  into  the bottom  of  the
test container at the rate of 100 mis. per hour.   The used mixture
overflowed the top of the container at the same rate.  The test period
was 96 hours.  Dissolved oxygen was determined  by the modified  Winkler
method before the snails ware introduced.  Two  D.O.  readings were made
during each 24-hour test period.

Conditions of the Tests
     Same as Fish Tests.

Addition of Test Organisms
     Twenty adult snails were added to this mixed solution as soon as
the dissolved oxygen had been raised to the required level.

Control
     Same as with Fish.

Calculation of the Biologically Safe Concentration
     Same as with Fish,

     3.   Diatom
          The Test Organism  -  Navicula seminulup var. hustedii Patr.,
 is a moderately sensitive  fresh-water diatom common to many undis-
 turbed streams.
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      The diatoms were cultured for several months prior to the test
 period in 500 ml Erlenmeyer flasks, containing soft water nutrient
 solutions.
      These stock cultures were maintained at 18C  1C.  Light,  an
 important factor in the growth of diatoms, was provided by two 85 watt
 daylight fluorescent lamps located .about six inches below a glass
 shelf, furnishing an illumination of approximately 250-350 foot candles.
 The cultures were placed on the shelf, and received 16 hours of this
 illumination.  Cultures were agitated constantly to insure even dis-
 tribution of the diatoms throughout the flask.

 Apparatus for Tests
      The batch tests were conducted in sterile 125 ml Erlenmeyer
 flasks.   In each of the specific concentrations of sample in dilution
 water there was a total of 50 mis of liquid.  This provided a relat-
 ively large surface-to-volume ratio,  and thus allowed full exchange
 of gases  in the air.

 Conditions  of Tests
      Temperature:      18C + 1C.
      Light:            250-350 foot candles and as for stock cultures
                       above.
      Dilution water:   Same as  Fish with the addition of soil extract
                       and  micrometabolic solution.

Agitation
     The batch tests were  placed on a  shaker during the 7-day test
period to insure an  even distribution  of the diatoms.
                                140

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Addition of the Test Organisms
     The Inoculum was made uniform with the use of a Waring Blender.
One milliliter of the inoculum is pipetted into each test flask.  After
seven days each fiask is scraped clean and the coiitents blended.  Then
cell counts are made of diatoms.  These counts are compared to the con-
trol to determine the reduction in growth.

Calculation of the Median Tolerance Limit
     In calculating the effect of any sample, the concentration which pro-
duced a 50 percent reduction  in growth is considered as significant for
diatoms.
     In most cases no concentration in these tests produces exactly a 50
percent reduction in growth,  and it is usually necessary to determine this
value by graphic interpolation of the test results.  The 50 percent reduc-
tion in growth concentration  corresponds  approximately to the median toler-
ance limit (TLm) for fish.

IV.  CHEMICAL, PHYSICAL AND TOXICOLOGICAL PROPERTIES
A.   Chemical and Physical Propartleg
Characterization and standardization of detergent ingredients is par-
ticularly important because small differences  in purity or composition
often make a big difference in  performance.  Chemical  characteriza-
tion includes assurance and reproducibility  of molecular structure,.
 stability against hydrolytic  or oxidative decomposition or other
 types of chemical change under  storage or use  conditions, and quan-
 titative knowledge of minor contaminants  that  may have a significant
 effect on overall behavior.   On this basis we  propose  to check  the
 various ingredients used  in the detergent formulations in the  follow-
 ing manner.  Manufacturers and  suppliers' specifications with regard
                                 141

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 to chemical structure will be used except when they are inadequate
 (incomplete) or where we have reason to suspect that they are inac-
 curate.  In such cases, using ASTM methods of test wherever available,
 the following characterization tests will be applied:   Builders will
 be checked for sequestering power by the soap or oxalate titration
 methods given for example in Chabarek and Kartell "Organic Sequestering
 Agents," or by other appropriate methods.  Surfactants will be checked
 for active ingredient content and neutral oil (unsulfonated matter)
 content.  Polymeric materials will be checked by viscosity for average
 molecular weight (paying attention to polyelectrolyte effects in the
 measurements)  and by chemical analysis for degree of substitution
 (where indicated).  If indicated, gel permeation chromatography will
 also be used.   All major ingredients will be checked for trace ele-
 ments, using atomic absorption spectroscopy and/or emission spectral
 analysis.   This is considered important because trace elements can
 have a significant effect on the biological effects of the product,
 particularly the biostimulation.  Final formulations will require
 checking for stability,  since many detergent ingredients tend to
 suffer hydrolytic degradation during drying or other stages of pre-
 paration.   Tests for degree of degradation are routine but they vary
 with the type  of surfactant or builder involved.
 Physical properties  of  importance include solubility and rate of
 solution at various  temperatures,  bulk density,  dustiness,  and phy-
 sical  homogeneity.   Physiological effects of the  final formulations
 are obviously of  paramount  importance.   These include  toxicity (by
 ingestion as measured by  LD-50 values  on test aminals)  skin irrita-
tion and sensitization and  eye irritation.   They  will  be determined
by methods  outlined  below.

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B.   Toxlcological Properties
Background - A toxicity testing program to evaluate the safety of de-
tergents must be designed to include the intended use of the product.
Obviously, testing of a detergent composition intended for general use,
such as laundering and dishwashing,  has to be more inclusive than of
one intended just for machine laundering.   A general purpose household
detergent product can be evaluated by methods similar to those descri-
bed by Snyder et.al. (1964) and Opdyke et.al. (1964).  These include:
acute oral toxicity and emetic dosing to evaluate accidental ingestion
hazards; chronic oral toxicity to evaluate ingestion from residues on
dishes and cooking utensils; subacute percutaneous toxicity to evaluate
continuous exposure to skin from residues on hands and clothing; human
patch test studies to evaluate the irritancy or sensitization poten-
tial of the detergent; opthalmic irritancy in rabbit eyes to determine
the hazard to eyes from accidental exposure; and tumorigenic activity
as measured by repeated topical and subcutaneous applications to mice.
Because we propose only preliminary testing, in preparation of a con-
sumer test, our proposal below is not so all inclusive.

Test Methods -  The studies proposed here are sufficient to evaluate,
in a preliminary way, the medical safety of a heavy-duty household de-
tergent composition intended for machine laundering.  The animal tests
listed below by themselves are intended to screen the medical suit-
ability of an ingredient for including in household product.  The
combination of these animal tests and the human studies described
below are designed to evaluate the detergent to a degree sufficient
for a Consumer Test where human exposure is  limited  in numbers  (say
up to 500 people) and in duration (say up to one month of normal use).
More complete testing would be necessary before the  formulation should
be sold to larger numbers of people.

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 Acute Oral Toxicity - Healthy, young albino rats ranging in body
 weight from 125 to 200 grams will be used as test animals.   All
 animals will be kept under observation at least seven days  prior to
 experimental use, during which period they will be checked  for gene-
 ral physical health and suitability as test animals.   The animals will
 be housed in stock cages and permitted a standard laboratory rat diet
 plus water ad libitum until 16 hours immediately prior to oral in-
 tubation.
 Initial screening will be conducted in order to determine the general
 level of toxicity and then selected dose groups of four rats each
 (two male and two female) will be intubated with previously calculated
 doses of the test material.  All doses will be administered directly
 into the stomachs of the rats using a hypodermic syringe equipped with
 a ball-pointed intubating needle.
 Following oral administration of the test material, the rats will be
 housed individually in observation cages (10" x 8" x  8") and observed
 for the succeeding 14 days.  Initial and final body weights as well
 as  all mortalities and/or reactions displayed will be recorded.
 Arrangements will be made to autopsy any animal which might succomb
 during the study as well as all surviving animals at  the end of 14 days.
 At  the end of  the observation period,  all data will be collected and
 arrangements will be made to calculate,  if possible,  the acute oral
 median lethal  dose (UDc0)  of the test  material using  the techniques
 of  Weil  (1952),  Thompson (1947),  and Thompson and Weil (1952).

Acute Dermal Toxicity -  Young  adult, New Zealand strain albino rab-
bits ranging in  body weight  from 2.3 to  3.0  kilograms  will  be em-
ployed as test animals.  All rabbits will be kept under observation
in the laboratory  for seven days  prior to testing during which time
                                144

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the animals will be examined with respect to their general health
and suitability as test animals.  The rabbits will b housed indivi-
dually in hanging rabbit cages and maintained on a standard laboratory
rabbit ration.  Food and water will be permitted ad libitum.
Twenty-four hours prior to the dermal applications, the backs of the
rabbits will be shaved free of hair with electric clippers.  The
shaved area on each animal will constitute about ten percent of the
total body surface area.  The animals will then be returned to their
cages to await testing on the following day.  The 24-hour waiting
period will allow recovery of the stratum corneum from the disturbance
which accompanies the close-clipping procedure and also will permit
healing of any microscopic abrasions possibly produced during the pro-
cess.
                                                                    /
On the testing day, the rabbits will receive skin applications of
the test material at several selected dose levels.  Groups for each
dose level will consist of four rabbits  (two male and two female).
After each application, the exposure site will be covered by wrapping
the trunk of the animal with an impervious plastic sheeting which
will be securely taped in place.  This plastic wrap will insure in-
timate contact of epidermis and test material.  To further prevent
oral ingestion of the test material, each animal will be fitted with
a lightweight flexible plastic collar which will be worn throughout
the observation period.
The test material will remain in  contact with the  skin for 24 hours.
Any reaction displayed by the animals will be observed and recorded,
during the contact period, after  which the plastic sheeting will be
taken off each test rabbit and  all  residual  test material  removed.
The exposure sites will be examined for  local skin reactions and the
animals returned to their cages.   Observations  for mortality,  local
                               145

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 skin reactions,  and behavioral abnormalities  will  be  continued  for a
 total of 14 days following the skin applications.   Initial  and  final
 body weights will also be recorded.   Arrangements  will  be made  to
 autopsy any animals which might succumb during the study as well as,
 all surviving animals at the end of the observation period.
 At the end of the observation period,  all  data will be  collected and
 arrangements made to calculate,  if possible,  the acute  dermal median
 lethal dose (U5cQ)  of the test material using the  techniques of Weil
 (1952),  Thompson (1947),  and Thompson and  Weil (1952).

 Opthalmic  Irritation -  Five young adult albino rabbits  of the New Zeal-
 and strain will  be  used to evaluate  the eye irritating  properties of
 the test material.
 The test method  employed will be patterned after that of Oraize et al.
 (1944).  Exactly 0.1 ml or 0.1 g of  a test material will be instilled
 into the conjunctival sac of the right eye of each test rabbit.  The
 left eye of each animal will serve as  a scoring control.
 One,  24, 48,  72,  96  hours,  and 7 days  following the initial instil-
 lations, the  cornea,  iris,  and palpebral conjunctiva  will be examined
 individually  and  graded for irritation and injury  according to  a stan-
 dard  scoring  system.  The maximum possible score at any one examination
 and  scoring period is 110 points which indicates maximal irritation.,
and damage to all three ocular tissues.  Zero  score indicates no ir-
ritation whatever.   The scoring  system is  presented in  the  following
Table.
                               146

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               Eye Irritation Test - Albino Rabbits

Scale of Weighted Scores for Grading the Severity of Ocular Lesions


I.   Cornea

     A.   Opacity - Degree of Density (area which is most dense
 *(        is taken for reading)
 Jf       Scattered or diffuse area - details of iris clearly
          visible                                                 1
          Easily discernible translucent areas,  details of
          iris slightly obscured                                  2
          Opalescent areas, no details of iris visible, size
          of pupil barely discernible                             3
          Opaque, iris invisible                                  4

     B.   Area of Cornea Involved.
          One quarter (or less) but not zero                      1
          Greater than one quarter but less than one-half         2
          Greater than one-half but less than three quarters      3
          Greater than three quarters, up to whole area           4

          Score equals A x B x 5   Total maximum = 80


II.  Iris

     A.   Values
          Folds above normal, congestion, swelling, circum-
          corneal injection  (any  or all of these or combina-
          tion of any thereof), iris still reacting to light
          (sluggish reaction is positive)                         1
          No reaction to light, hemorrhage, gross destruc-
          tion (any or all of these)                              2

          Score equals A x 5       Total maximum =  10
 III. Conjunctiva

     A.   Redness  (refers  to palpebral  conjunctiva only)
          Vessels  definitely injected above normal                 1
          More diffuse,  deeper crimson  red, individual
          vessels  not easily discernible                           2
          Diffuse  beefy  red                                       3

                                 147

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         Eye Irritation Test  - Albino Rabbits  (Continued)
 III.  Conjunctiva

      B.    Chemosis
           Any swelling  above  normal  (includes nictitating
           membrane)                                               1
           Obvious swelling with partial eversion of the lids      2
           Swelling with lids  about half closed                    3
           Swelling with lids  about half closed to completely
           closed                                                 4

      C.    Discharge
           Any amount different from normal  (does not include
           small  amount  observed in inner canthus of normal
           animals)                                                1
           Discharge with moistening of the  lids and hairs
           just adjacent to the lids                               2
           Discharge with moistening of the  lids and hairs
           and  considerable area around the  eye                    3

           Score  (A = B  = C) x 2    Total maximum = 20
Note:  The maximum total score is the sum of all scores obtained for
       the cornea, iris and conjunctiva.
                              148

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Rabbit Primary Skin Irritation - Four young adult albino rabbits of
the New Zealand strain will be used in the evaluation of primary skin
irritating properties of the test material.  The test procedure em-
ployed will be modeled after that of Draize et.al. (1944).
Prior to the application of the test material, the hair will be clip-
ped from the backs and flanks of each rabbit.  Two test sites located
at the midline of the back approximately ten centimeters apart will
then be selected.  One of the two sites will be abraded by making
four epidermal incisions, two perpendicular to the other two, while
the other skin site will remain intact.
Exactly 0.5 ml or 0.5 g of the test material will be applied to the
prepared exposure sites on each rabbit and immediately occluded with
square gauze patches, two inches on a side.  These will be affixed
directly over the skin test sites and secured in place with masking
tape.  Following the patch applications, the entire trunk of each
test animal will then be wrapped in an impervious plastic sheeting.
This will help hold the patches in position and retard evaporation
during the 24-hour exposure period.
At the end of 24 hours, the plastic wrappings and patches will be
removed.  The intact and abraded skin sites will then be individually
examined and scored separately  for both erythema and edema on a
graded scale of 0 to 4.  After  72 hours had elapsed, the sites will
be re-examined and rescored.
In evaluating the average irritation present, the mean scores for
erythema and edema of the intact skin sites at the 24- and 72-hour
reading intervals will be added.  Similarly the mean scores  for
erythema and edema of the abraded skin  sites  at the 24- and  72-hour
reading intervals will be added.  These two values will then be
totaled and divided by four to  obtain the  mean primary irritation

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 score.  The scoring criteria for erythema and edema are shown in

 the following Table.
 Reaction
 Erythema
 Edema
                             Table
SCORING CRITERIA FOR SKIN REACTIONS

               Description                        Score

       Barely perceptible
         (Edges of area not defined)                 1

       Pale red in color and area definable         2

       Definite red in color and area well
         defined                                    3

       Beet or crimson red in color and/or          4
         injury in depth (necrosis, escharosis)

       Barely perceptible
         (Edges of area not defined)                 1

       Area definable but not raised  more            2
         than 1 mm

       Area well defined and raised                 3
         approximately 1 mm

       Area raised more than 1 mm                   4

       Maximum Primary Irritation Score =            8
Human Primary Irritation  and  Sensitization -  Semi-occlusive Patch Test

Procedure, 9-Day - 24 hours.   (Eight repeated insults plus one chal-

lenge patch.)

This is a combined over-night primary irritancy and/or sensitization

test.  Patches are applied Monday, Tuesday, Wednesday, and Thursday

to the same skin sites and allowed to remain  on for 24 hours.
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Readings are made shortly after the patches are removed on Tuesday,
Wednesday, Thursday and Friday.  Following two weeks of patching
and two rest weeks, a challenge patch is applied and readings taken
at 24, 48 and if necessary at 72 hours.
A panel of 50 subjects are employed on this test.  Four materials
including controls can be run on this test.  Two types of patches
are used on this test:  1) Closed elastopatch (Duke) 1-1/2" x 2"
with 3/4" x 1" special pad and 2) Semi-open elastoplast (Duke) pro-
tective covering for patch test 1" x 2" with 1" x 1" Webril (R) pad.
The material is applied to the patch which is then placed on the sur-
face of the upper arm.  A marker (Gentian Violet) is used to indicate
the patch position on the arm.  Readings are taken approximately 24
hours after each patch application.  Following each reading, a new
patch is applied to the same unless the severity of the reaction pro-
hibits repatching.  For the challenge application, patches are ap-
plied to adjacent sites on the arm.  A second challenge is made if
there is a reaction to the first.
In most, if not all instances, the test product will be a solid mate-
rial.  For the tests described above, it will be applied to the ani-
mal as a dilute, aqueous solution, approximately 5 percent wt/vol.
For human testing, the products will be tested as 1 percent wt/vol.
aqueous solution.
                              151

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 References - Preliminary Mammalian Toxicity Testing

 Draize,  John H. ,  Woodard, Geoffrey,  and Calvery,  Herbert 0.  (1944).
 Methods  for the  study of irritation and toxicity of substances ap-
 plied topically  to the skin and raucous membranes.  J.  Pharm.  and
 Exp.  Ther., 82,  377.
 Opdyke,  D. L. , Snyder, F. H. ,  and Ruberkoenig,  H. L. (1964).   Toxi-
 cologic  studies  on household synthetic detergents.  II.   Effects on
 the skin and eyes. Toxicol. Appl. Pharmacol.,  , 141-146.
 Snyder,  F. H. , Opdyke, D. L. ,  Griffth, J.  F., Ruberkoenig, H. L. ,
 Tusing,  T. W. , and Paynter,  0. E. (1964).   Toxicologic studies on
 household synthetic detergents.  I.   Systemic effects.  Toxicol.
 Appl.  Pharmacol.  j>, 133-140.
 Thompson,  W.  R.  (1947) .  Use of moving averages and interpolation to
 estimate median-effective dose.  Bait. Rev. 11, 115-145.
 Thompson,  W.  R. and Weil, C. S. (1952). On the construction of tables
 for moving average interpolation.  Biometrics,  JJ, 51-54.
 Weil,  C.  S.  (1952).   Tables  for convenient calculations  of median-
 effective  dose (H>rO
metrics, , 249-263.
effective dose  (H>rO or E1)c0) aiu* *-nstruct*-ons  *-n their use.  Bio-
                            152

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   Provisional Test For Screening Potentially Corrosive Products

Method
     Four healthy, adult, albino rabbits of either sex (weight range
2-3 kg.) will be used to test each material.  The animals will be
fasted for 48 hours prior to testing with water available ad libitum.
                                '2
Each animal will be anesthetized  with sodium pentobarbital, and the
oral cavity will be examined with the aid of a binocular loupe (mag-
nification 2-3X) and examining lamp.  After recovery from anesthesia,
the animals will be placed in a restrainer, and the mouth forced open
with a plastic bit containing a 1/2" to 3/4" hole in the center.  The
tongue will be drawn forward through the hole with a pair of long
forceps.  A curved spatula or syringe will be used to administer the
dose (300-500 mg. of dry material, or 1 ml. of liquid) on the posterior
aspect of the tongue.  The tongue will be released immediately allow-
ing the animal to complete the swallowing reflex.  The animal will be
returned to its' cage with access to water, but no food.  At 24 hours,
two of the test group will be sacrificed by overdose of anesthetic
(pentobarbital IV).  The surviving animals will be given food, and
sacrificed at 96 hours.  The tongue, adjacent pharyngeal structure,
esophagus., and stomach will be removed, examined grossly, and photo-
graphed (color).  After thorough evaluation, these tissues will be
preserved in neutral buffered formalin for subsequent microscopic
evaluation as necessary.
     Evaluation for corrosivity will be based on visible effects on
the oral cavity, pharyngeal structure, esophagus, and stomach.  Each
test material will be arbitrarily classified as follows:
1.   This is not an official test procedure.
2.   If the animal's mouth can be examined easily without any discom-
     for or anesthetic, the problems of anesthesia can be eliminated,
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      a.    Negative  -  No visible  irritation or  injury when examined at
           24 or 96  hours.   Histopathology may  not be necessary as de-
           termined  by gross examination.
      b.    Irritant  -  Patchy areas  of beefy redness with or without
           edema present at  24 hours, but  not at 96 hours.  Histological
           examination of tissue  from the  animals sacrificed at 96 hours
           should be normal  in appearance.
      c.    Corrosive -  Necrotic lesions  (i.e.,  esophageal perforation,
           stricture,  etc.)  apparent at  24 or 96 hours will be con-
           firmed by microscopic  examination.
      Since the  test is  primarily concerned with corrosive action, it
will  be considered  positive if any of the test animals at 24 or 96 hours
show  signs of necrotic  lesions in  the mouth, pharynx, esophagus, or
stomach.   The extent  of injury will be  confirmed by histological ex-
amination.  Microscopic examination of  tissue  sections will not be
performed  in the absence of visible irritation.  Close-up photographs
will be considered  as sufficient documentation.  When gross lesions
are present or  for  borderline cases, histopatholgy will be performed
in addition to photographs.  Color photography will be utilized as
often as warranted  to provide a vivid documentation of gross effects.
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                           APPENDIX B
              IAUNDERING TEST METHODS DEVELOPMENT

Detergent technologists and scientists have never been able to agree
upon any single simple laboratory test for measuring the soil removing
power (laundering effectiveness or washing power) of a detergent.
The basic experiment is simple and straightforward in concept.  A
set of fabric swatches is soiled in some controlled manner to a uni-
form degree of dirtiness.  Some of the swatches are then washed in
detergent A and others in detergent B, keeping the detergent concen-
trations, temperatures, and other parameters of detergency constant.
The washed swatches are then measured optically to determine which have
lost more soil.  Disagreement arises over details of the test, es-
pecially over the type of soil that is used and the method by which it
is applied to the swatches.  Each of the important laboratories of the
detergent industry has its own screening protocols and its own pro-
cedures for obtaining detergency data that they consider accurate
(i.e. representative of results that will be obtained in actual home
laundry practice).  The details of these methods are not publicly
divulged.  The one method for evaluating washing power that is agreed
upon is an actual miniature field trial under household conditions,
known as the bundle test.  This test has been reasonably well stan-
dardized, at least in general format, and is described as ASTM Stan-
dard D2$60-71T.  The bundle test, however, is far too lengthy and cum-
bersome to be used as a test method in research.  It was therefore
necessary to adopt  (or develop if necessary) a set of screening pro-
cedures that would at  least be respected by all major segments of
the industry even though it might not coincide with their own favo-
rites.  Throughout the program, therefore, special attention was paid
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 to refinement and variation of the test methods even though this re-
 quired a significant amount of laboratory work.  The lengthier  and
 more extensive testing programs were reserved for the more  promising
 candidate detergents, but modifications of the simpler tests were
 adopted as soon as they were proved to be valid and useful.  The various
 procedures, their modifications, and the experimental work  connected
 with their interpretation and validation are as follows:
 A.   The primary screening test for laundering effectiveness used in
 this program was a soil accumulation test, following the  general model
 given in articles by Schwartz and Berch, Soap and Chemical  Special-
 ties, 39, 78, (May,  1963); Spangler, Cross and Schaafsma, J. Am. Oil
 Chemists Soc. 42, 723 (1965); and Schwartz and Rader,  J. Am. Oil
 Chemists Soc. 42, 800 (1965).  In this type of test one or  more un-
 known detergents are compared against a standard detergent  under
 identical conditions of soiling and washing.  To illustrate the pro-
 cedure for one unknown detergent:   two identical sets of  clean  test
 swatches are soiled  simultaneously in a single large pool of soil.
 The  sets are then separated and washed separately,  one set  in the
 standard detergent "S" and the other in the unknown detergent "X".
 After washing and drying  they are  resoiled and again separated  and
 washed,  each set going to its own  detergent.  After several  cycles of
 soiling  and washing  the sets  are again measured for reflectance.  Even
 when two detergents  are very close in cleaning power a significant dif-
 ference  in  the  set averages  can usually be found after about 5  cycles.
 Included  with each set are some swatches that go through the washing
 and drying  steps  but  not  through the soiling step.   These swatches
 accumulate  soil by redeposition from the wash bath,  and the  decrease
 in their  reflectance  is a measure  of the antiredeposition effect of
the detergent.  A wide variety of  soils  can be used,  but some type of
"natural" soil is generally preferred.
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The Tergotometer was used as the washing device,  run at either 100 or
125 cycles/minute.  Three types of white fabric were used in the early
stages of the program:  a permanent press 65 polyester-35 cotton blend;
a bleached but unfinished cotton print cloth; and an unfinished 100%
polyester.  The three types of fabric were all washed simultaneously
in one bath, the load consisting of 3 soiled swatches and 2 redeposi-
tion swatches of each fabric, a total of 15 swatches in each one liter
bath.  The swatches measured about 4.5 x 6 inches and averaged about
2 grams each in weight.
Both the water hardness and the temperature can be varied as desired,
but must be controlled and specified in the report.  Our primary test
was made with 200 ppm water (4:1 Ca to Mg ratio)  at 120 F.  The washing
time was 10 minutes.  To ensure that the detergent was performing at
full effectiveness, i.e., that we were in the plateau region of the
soil removal v. concentration curve, the formulations were used at
0.3% concentration.
                                                        /
Two types of soil were used:  a "dry" soil and an "oily" soil, both of
which were based on the dirt swept from rugs by vacuum cleaning.  The
dirt was procured  in large lots  (20-50 pounds or more) from a commer-
cial rug cleaning establishment.  It was processed by slurrying in
tap water and then filtering through cheesecloth and muslin to remove
lint and large particles.  Quantity of water was  adjusted so that the
final filtered slurry contained about 2% solids.   The soil was also
checked to ensure that no soluble staining materials were present.
Batches of soil containing staining materials were rejected.  The
2% solids slurry thus prepared constituted  the "dry" soiling bath.
A small amount of preservative was added.   The "oily" soil was pre-
pared by adding sufficient artificial sebum, (prepared according to
Spangler, Cross and Schaafsma,  loc. cit.) to provide a sebum-to-so lid
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 soil ratio of about 2 to 1.  The water content was  adjusted  so that
 the final slurry contained about 1.5% sebum-plus  solid  soil.
 As standard detergents in these tests we used Formulation #124,  fur-
 nished by the American Association of Textile Chemists  and Colorists.
 This material is described as follows:

                       Standard AATCC Detergent
                          Lot 1-1 & Lot 2-1
 Nominal Composition
      Linear alkylate sulfonate - sodium salt (LAS)
      Alcohol ethoxylate
      Soap - high molecular weight
      Sodium Tripolyphosphate
      Sodium silicate (Si02/Na20 = 2.0)
      Sodium sulfate
      CMC
      Moisture & Miscellaneous
                                                               100.00

 In Standard Detergent with optical brightener (Lot  1-1  only) the mis-
 cellaneous  includes approximately .25% of a  mixed brightener system
 including balanced  proportions  of bis [triazinyl] stilbenedisulfonate,
 and triazolystilbenesulfonate with a potential specialty brightener.
 In the  earlier  phases  of  the  program Lot  1-1 was used,  and is refer-
 red to  in the text  simply as  AATCC or AATCC  #124 detergent.  At a
 later stage  Lot  2-1 was used.   This is  referred to  as AATCCWOB.
 Lot 1-1, which  contains brightener,  was the  only standard reference
detergent available at the  start  of the program, and it was con-
sidered desirable to use  in addition a  reference detergent without
brightener.  A supply of  such a detergent was  obtained  from The Asso-
ciation of Home Appliance Manufacturers.  This is referred to as the
                                158

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                'a
                fo
AHAM detergent, and has the following composition:
     Tallow Soap                               2%
     Dodecylbenzene Sodium Sulfonate          14%
     Nonionic Fluronic Type                    2%
     Sodium Tripolyphosphate                  50%
     Trisodium Silicate (2:1)                  6%
     NaCMC                                   0.5%
     Sodium Sulfate                           17%
     Water                                   8.3%
     Miscellaneous                           0.2%

B.   The above procedure, using "dry" and "oily" (or "sebum") vacuum
cleaner soil, was modified during the course of the program in two
respects, both of which simplified the testing and neither of which
changed the results to any significant extent.  The first modification
consisted in using only three wash-soil cycles instead of four.  At
the soil concentrations used it was found that three cycles were suf-
ficient.  The second modification was a change in the method of pre-
paring oily soil swatches.  Instead of combining the aqueous sebum
emulsion with the suspension of solid vacuum cleaner particulates and
soiling in a single step, a two step process was adopted.  In this
process the first step was to prepare dry soiled swatches in the usual
manner.  These were then wet to saturation with a perchloroethylene
solution of the artificial sebum ingredients, and were then air
dried.  This process afforded much*better control and produced more
uniform and reproducible swatches than the one step procedure.

C.   A third wash testing procedure adopted and used during the course
of the program was essentially that described by Spangler, Cross and
Schaafsma (J. Am. Oil Chemist's Soc., 42, 723  (1965).  This is a
159

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 multicycle soil-accumulation test of the same type as the tests de-
 scribed in section A above.  The soiling mixture is an aqueous emul-
 sion containing the artificial sebum ingredients and particulate
 solids obtained from air conditioner filters.  To prepare the solids
 portion of this mixture used air conditioner filters were washed with
 isopropanol.  This solvent stripped the filter fibers clean very rapid-
 ly and easily.  The washings were filtered on a Buchner funnel, and
 the recovered solids were dried and ground.  They were a very dark
 gray in color, very finely divided (requiring little or no sieving
 to remove lumps) and easily dispersed in the artificial sebum emul-
 sion.   This soil is referred to in the body of this report as
 "Spangler soil" and was always used in the three cycle soil accumula-
 tion procedure.

 D.    Primary screening test of washing power are usually made, as
 outlined above, at a single detergent concentration.  For a more
 thorough evaluation it is necessary to measure the washing power at
 a  series of concentrations.  This can be done using a multicycle test
 procedure,  as were some of the washing power evaluations in this pro-
 gram, but  it  is inordinately time consuming.  Single cycle tests are
 usually considered adequate for detergency v.  concentration studies.
 Soil cloth  suitable  for single cycle  testing can be purchased commer-
 cially.  In our experience,  however,  few if any of the man-made fiber
 soil cloths or the permanent press  finished soil cloths are suffic-
 iently  realistic or reliable.   One  commercial  cotton soil cloth,
 "Empa"  from Test fabrics,  Inc.,  New  York, was used in some of the deter-
 gency v. concentration  studies.   For most  studies of this type on
 cotton, and for all such  studies  on other  fabrics,  we prepared our
own soil cloth as  follows:
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     The soiling mixture was similar to the Spangler soil except that
the air conditioner dirt vas replaced by a mixture of particulates
consisting of 86% kaolin (Bandy Black #1 clay),  8% carbon (Germantown
Lampblack), 4% Mapico black iron oxide and 2% Mapico yellow iron oxide.
The aqueous soil suspension was applied by padding.  By setting the
pad rolls at a pressure (about 50 psi) such that the wet pick-up was
about 100%, and by running the fabric through the pad forward and
reverse twice, large single pieces of fabric were soiled uniformly
and reproducibly.  These could be cut into test-size swatches which
matched one another so closely in reflectance that they did not have
to be sorted nor read individually before use.   This is referred to as
"Colgate soil.11
      
E.   The instrument used for measuring reflectance was a Gardner XL-10
Color Difference Meter.  The filters are such that it can read green
(G) amber  (A) blue (B) and blue free of u.v. (Bx).  The three readings
made routinely were G, A and Bx.  The G reading by itself is generally
considered a good basis for comparing the appearance of cleanness
presented by a fabric swatch, and the delta G values were used for
comparisons in most of the earlier work.  From the three primary re-
flectance readings, however, two additional reflectance parameters
can be calculated:  "whiteness"  (W) = 4Bx - 3G; and "yellowness"
= A-Bx   This was done routinely in the computer program.  It was
   G
found after bundle testing had been started, and visual judgments
were being compared with instrumental readings, that the W value was
usually a better index than the  G value of the visual ratings.  The
W value was therefore adopted as the main basis for comparison.  The
Y value was important in cases where either the detergent or the fabric
finish changed the tint of the test swatches.  Such cases are noted
in the text.  Table headings in  all cases indicate which reflectance
parameter  is being considered.

                               161

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 F.   Bundle tests were made on seven formulations, the general pro-
 cedure of ASTM, D2960-71T being followed in all cases.  Rockville,
 Maryland, tap water, averaging 110 ppm, was used.  In the first three
 tests the detergent formulation was used at 0.2% concentration and
 instrumental readings were made only on pillowslips.  The formula-
 tions were as follows:  (1) #64-1, also identified as "D", based on
 citrate builder and ether carboxylate 60-486 surfactant.  (2) #64-2,
 also identified as "M", based on citrate builder and sulfozwitterionic
 surfactant 54-431.  (3) Composition B-S based on SHIM builder and
 alpha olefin sulfonate surfactant 22-155.  Two subsequent runs iden-
 tified as 242 and 242a were made at 0.15% concentration, with pillow-
 slips read instrument ally.  At this low concentration even the con-
 trol detergent AATCCWOB did not get the laundry satisfactorily clean.
 The last three tests identified as 269, 270 and 271, were therefore
 made at 0.3% concentration.  In these latter tests all laundered
 items were read instrument ally.  The instrumental readings checked
 the panel judgments without exception.

 G.    An essential part of the methods development program was to com-
 pare the three multicycle and two single cycle wash tests outlined
 above with one another and with the bundle test.  This task was
 carried out,  and was written up and presented in the form of a paper
 at  the  CID's  International Congress on Surface Activity, Zurich,
 September 1972.   Title and authors are:   "Soil Accumulation versus
 Bundle  Testing of Detergency," H.  Alter,  A.  Eleanor Davis and
A. M. Schwartz.   It  is scheduled  for publication in the Congress
Proceedings.   The  following is an abridgement of the paper.
EXPERIMENTAL
     Five test procedures were used.  Procedure #1 was single cycle
using Empa cotton.  Procedure  #2 was  single cycle  using Colgate soil.
                               162

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Procedure #3 was multicycle Spangler soil.   Procedure #4 was multi-
cycle "dry" vacuum cleaner soil, and procedure #5 was multicycle
"sebum" vacuum cleaner soil, as described above.   All except pro-
cedure #1 were carried out on both cotton and durapress (DP) 50 cotton:
50 polyester fabric.  The prepared swatches were  read on the re-
flectometer before and after washing.  Alcohol extractable material
was determined on washed swatches and on representative swatches be-
fore washing.
     The Tergotometer load consisted of 10 swatches, 6 soiled and
4 unsoiled  (redeposition) swatches.  In all but procedure 1 the load
was split evenly between cotton and durapress swatches.  The volume
of detergent solution was 700 ml, and the pH of the detergent solu-
tion was checked before and after washing.  Agitator speed was
125 cycles/min.  Wash temperature was 120F and wash time 10 minutes.
The swatches were given two one minute rinses at 105F.  After rinsing
the swatches were squeezed out, spread flat on cheesecloth and oven
dried at 120F for  15-20 minutes.
     Reflectance was measured  at 4  areas (2 front and 2 back) on each
swatch.  The swatches were  layered  and folded for measurement to pro-
vide 5 thicknesses  of backing  for  soiled swatches and 3 thicknesses
for redeposition swatches.  Readings were made with green, amber and
blue X filters.  The data were automatically punched into computer
tape for processing.
     Alcohol extractable matter was measured  in  the  standard manner
via Soxhlet extraction with ethanol.
     Three  detergents were used in the bundle tests.   The primary
 standard-of-comparison detergent was the high phosphate formulation
 furnished as a reference  by the Association of Home Appliance Manu-
 facturers  (Identified as  AHAM detergent).   This  material contained
                                163

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 no fluorescent whitening agent.  The other two detergents were  ex-
 perimental nonphosphate materials.   Both contained 20 percent high
 ratio silicate and 30 percent citrate as the builder.   "Detergent D"
 contained 20 percent fatty alkyl ether carboxylate as  the surfactant.
 "Detergent M" contained 20 percent  of sulfo-zwitterionic surfactant.
 Both detergents contained 1 percent sodium carboxymethylcellulose,
 29 percent sodium sulfate, and no fluorescent whitening agent.
      The above three detergents were also used in the  Tergotometer
 tests,  together with another high phosphate type furnished  by the
 American Association of Textile Chemists and Colorists identified as
 AATCC #124 and herein abbreviated "AATCC".   Detergent AATCC contained
 brightener (fluorescent whitening agent) and was therefore  not  used
 in the  bundle tests  where the ratings are subjective.   It was used in
 all the other tests  where the ratings were  instrumental, and the ef-
 fect of brightener could be eliminated by using the green and/or Bx
 filter  in the reflectometer.
      The bundle tests  were run at 0.2 percent detergent concentration
 in tap  water  (approx.  110 ppm hardness)  at  50C.   In all other  re-
 spects  the  conditions  of ASTM D 2960-71T were followed.  The Tergo-
 tometer tests  were run at 0.1 percent,  0.2  percent and 0.3  percent
 concentration;  in 200  ppm hard water (4 Ca  to 1 Mg)  as well as  in
 tap water.  All tests  were run at the same  temperature, time of wash
 cycle,  and  agitator  speed.

RESULTS AND DISCUSSION
Bundle  Tests
     The bundle  tests  (0.2  percent  concentration in tap water)  were
carried out to  six cycles.  The panel rated  detergent  D substantially
equal to AHAM on both  cotton  and  durapress  items.   It  rated detergent
                               164

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M clearly inferior to AHAM on both fabrics.   Analysis of the data for
detergent D with regard to fabric type showed that the panel chose
AHAM somewhat more frequently than D on cotton items, and vice versa
on durapress items.
     Instrumental readings were made on pillowcases of both fabrics.
The data, as shown in Table BG1, supports the subjective evaluations.
D and AHAM are essentially equal in yellowness on both fabrics and
in whiteness on durapress.  D is very slightly inferior to AHAM in
whiteness on cotton.  M is significantly inferior to AHAM in white-
ness on both fabrics and slightly inferior in yellowness on cotton.
     There are many ways in which the reflectance data might be com-
bined to give a single number purporting to correlate with the panel's
subjective rating.  No such combination, however, would be entirely
free of arbitrary factors.  It appears that graying was considerably
more important than yellowing in this bundle test, but is entirely
possible that with strongly yellow soils the yellowness rating would
become more important and could dominate in correlating with the
panel judgment.
     It is noteworthy that the bundle test gives no  indication of
the amount of invisible soil, solid or oily, remaining in the fabrics
after washing.  The Tergotometer tests as performed  in this study
provide a direct measure of oily soil removal, via alcohol extrac-
tion.  No measurement was made  of residual invisible, alcohol-insol-
uble soil.

Tergotometer Tests Relatable  to Bundle Tests
     Tests using procedures 1 and 2 were carried out on  cotton and  on
durapress at 0.2% concentration in  tap water using the same  three de-
tergents used  in the bundle test.   The results of  these  tests are
                               165

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 therefore most directly comparable with the bundle test results.
 Procedures 3, 4, and 5 were carried out on both fabrics with the  same
 three detergents at 0.3% concentration in tap water,  and are there-
 fore comparable except for the difference in concentration.   This
 difference can be considered minor since in tap water the detergency
 plateau of these detergents appears to be reached at  a concentration
 less than 0.2%.  Tergotometer tests at other concentrations  and water
 hardnesses can be related only indirectly to the bundle tests.
      Table B62 presents the data for detergent D on cotton at 0.2%
 in tap water obtained by procedures 1 and 2.  Columns 2,  3,  and 4
 show the delta 6,  delta whiteness and delta yellowness values (in
 reflectance units)  relative to AHAM detergent.  These values are  com-
 puted as reflectance of AHAM washed sample minus reflectance of deter-
 gent D washed sample.   Thus,  a positive value means that AHAM was
 brighter,  and a negative value that D was brighter.  It is evident
 that the differences in yellowness are negligible and that the  dif-
 ferences in delta  6 and delta whiteness parallel each other  reason-
 ably well.   In view of the low yellowness values, ratings can safely
 be  based on the whiteness ratings.  On this basis procedure  1 rates
AHAM best,  followed in order  by AATCC,  M and D.   The  first three  de-
 tergents are  quite  close to one another and D would be considered
 slightly but  significantly poorer than AATCC or  AHAM.
      Columns  5  and  6 of Table B62 give the actual percentage of al-
cohol extractable material in the D washed swatches before the  first
machine washing and  after  the last washing.   Column 7  shows  the com-
parison between AHAM washed samples and D washed samples.  The  num-
ber in column 7 is obtained by subtracting the column 6 value for
D from the Column 6 value  for AHAM (not shown in the Table),  i.e.
               Column 7 =  Column 6  AHAM -  Column 6  D
                              166

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Thus,  a negative value in column 7 indicates that the oily soil con-
tent of D washed material was higher than that of AHAM washed mate-
rial,  i.e. AHAM was the more effective in removing oily soil.  The
oily soil is a relatively low 1.19%, and none of the detergents was
outstandingly effective in removing it.  Although the data indicate
AATCC most effective, followed in order by AHAM, D and M, the dif-
ferences are small.
     Procedure 2 rates the detergents with regard to whiteness in the
order M best, D, AATCC and AHAM tied for poorest.  With regard to
oily soil removal there is substantially no difference between any of
the four detergents.  It is noteworthy that in procedure 2 the un-
washed swatches have a relatively high content of alcohol extract-
ables, a goodly portion of which remains after washing.  Table B62A
gives the reflectance comparison of the redeposition swatches.  It
is evident that the differences are small as compared with the dif-
ferences in reflectance of the soiled swatches.
     Tables B63 and B63A give the numerical reflectance data for pro-
cedure 2 on durapress fabric.  The differences are of the same order
as those obtained on cotton.  Tables BG4 and BG4A give the data for
procedures 3, 4 and 5 on cotton at  .3% in tap water; Tables B65 and
B65A give similar data on durapress fabric.
     A comparison of bundle test results with results of testing by
the five different washing procedures  leads to the following conclu-
sions:  1.  The whiteness reading, rather than the yellowness or in-
dividual filtered readings, is the most realistic single basis for
relating to subjective judgment of appearance.  2.  Soiled swatches
are better than redeposition swatches  as a basis  for Judgment.  3.  Dif-
ferences in whiteness values less than about  1.5  are not significant
and do not correspond to a difference  discernable by the panel judges.
                                 167

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 This finding is supported by our previous experience.  4.   With re-
 gard to alcohol extract able material, we have no basis* for setting
 any numerical limit of significance on the delta values.   We can rank
 the detergents as to their effect in removing oily soil,  but whether
 or not these rankings have practical meaning is still an unanswered
 question.
      Table BG6 shows the ranking of the various detergents on the
 basis of whiteness.  The vertical bracket lines indicate a numerical
 difference between the bracketed items of less than 1.5 whiteness
 units.   It is evident that procedures 1 and 2 are not sufficiently
 discriminating;  although both procedures, when they do discriminate,
 do put  AHAM ahead of M and D.  In the one test where M and D are
 significantly different however (procedure 2, 0.3%, DP) they rank in
 opposite order to the bundle test.  Procedures 4 and 5 definitely
 favor the non-phosphate detergents over the phosphate, a result op-
 posite  to that of the bundle test.  Procedure 3 appears to match the
 bundle  test results more closely than any of the other procedures.
 This  may indicate that the air conditioner soil of procedure 3 is a
 better  simulant  than procedure 4-5 vacuum cleaner soil, at least for
 the soil in these particular bundle tests.

 Tergotometer Test not Directly Related to Bundle Tests
      Table BG8 comparing procedures 3,  4 and 5 in hard water at 0.3%
 detergent concentration,  also indicates procedure 3 to be  a better
 match than 4 or  5 for these  bundle tests, although the conditions are
 not comparable.   Table B68 indicates that results in hard  water tend
 to be much the same  as  in softer water,  at least within the tested
 range.  This  is borne  out by Table B69  which shows the comparison of
 detergents M and D at  increasing concentrations in hard water.   The
M and D ratings here can  be  compared with those of Table BG6.
                                 168

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     Since a single cycle procedure is  less arduous than a multi-
cycle,  and therefore would be desirable,  an extended study of pro-
cedures 1 and 2 was made, with results  shown in Table BG7.  It is evi-
dent that procedure 1 is quite consistent, and sensitive neither to
concentration nor water hardness.  In rating M above D, however, it
does not match the bundle test.  This is  probably due to the fact that
the carbon black soil of procedure 1 is not a good simulant for the
visible soil in the laundry bundles.  Procedure 2 appears to be quite
sensitive to both concentration and water hardness.  Procedures 1 and
4 use low-oil soils, and procedures 2,  3  and 5 use high-oil soils.
Tables BG2-BG5, together with extensive data on these systems not
herein presented, indicate that an unsatisfactory amount of oil re-
mains in the washed swatches when the high-oil soils are used, re-
gardless of what detergent is used.  Furthermore, the presence of ex-
cessive oil in the soil does not appear to contribute to consistency
of results ( as regards variations in hardness and concentration) nor
to realism in matching the bundle test.
     Redeposition data were obtained for all the tests tabulated.  They
generally bear out the data of Tables BG2A-BG5A, indicating that a
high carboxymethylcellylose content improves the redeposition on cotton,
and that redeposition is a much less sensitive index of performance
than soil removal.
               i
Conclusions
     None of the procedures and soil mixtures used in this study has
fully simulated the bundle test, although procedure 3 using air con-
ditioner dirt as the colored  soil  ingredient is a reasonably good
simulant.  There is an indication  that a  single cycle procedure could
be satisfactory if the right  solid colored soil component were used.
                                169

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 Neither carbon black nor the mixture of procedure 2 is completely
 satisfactory.  It is probable that a more detailed knowledge of  the
 colored solid components of the "natural" soil would be useful in
 this regard.  Of the two solid soils used in the multi-cycle procedures
 air conditioner dirt appears to be a more realistic simulant than
 vacuum cleaner dirt.  This may, however, be true only for the type
 of soil accumulated in these particular bundle tests.  The ratio of
 oily soil to solid soil in the mixture appears to be a factor of
 relatively minor importance, as evidenced by the similarity of the
 effects of procedures 4 and 5.  A large proportion of the oily portion
 of a high-oil soil remains in the fabric, even after most of the  colored
 soil components have been washed out.  The excess oil may have an ad-
 verse influence on the consistency of the test,  particularly on  its
 sensitivity to variations in hardness and concentration, as evidenced
 in Table BG7.  Detergent concentration and water hardness have less
 effect on detergent ranking than might be expected.  The overlaps and
 crossovers in ranking are not unexpected in the single cycle tests.
 In the multi-cycle tests they indicate that more cycles are needed,
 even after significant differences among the detergents begin to appear.
      Since the bundle test is multi-cycle it is logical to expect
 that a multi-cycle test would be the best simulant.  The data support
 this view,  and in the present state of the testing art multi-cycle tests
 appear more reliable than single-cycle.  The most important factor
 in simulation appears to be the colored components of the 'solids in
 the soiling mixture.   These should ideally be identical in chemical
 composition and  in particle size range to the colored components of
 the  natural soil  deposited on laundry.   There have been many excel-
 lent  studies on  soil  composition,  but few reports we are aware of
 on the  nature  of  the  soil  that  causes gradual graying of laundry on
 repeated usage-washing  cycles.   More work in this field would ob-
viously be  a valuable contribution.   In the meanwhile the air
                                  170

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conditioner soil of procedure 3 (rating AHAM over D and M)  and the
vacuum cleaner soil of procedure 4 (rating D over M) appear to offer
the closest and most consistent simulation of he bundle test.

H.   One of the important questions in modern practical detergency is
the effect of permanent press treatment on the washability of cotton
and polyester fabrics, and on blends of these two fibers.  Since
this laboratory is equipped to apply permanent press finishes under
controlled conditions, a study could be and was undertaken to de-
termine this effect.  Five fabrics were used in the study:   an un-
finished cotton (Testfabrics #400 M print cloth); an unfinished Dacron
batiste (Testfabrics #707); these same two fabrics with a permanent
press finish applied as described below, and purchased 50:50 cotton-
polyester Cannon sheets permanent press finish (the same "blend fabric"
used in most of the presently reported studies.  The finish applied to
the cotton and Dacron was as follows:
     Permafresh 114B                6% ow fabric
     Velvamine 732                    .33% ow  fabric
     Catalyst KR                   25% ow resin
     Triton X-100                   2% ow bath
     Water to 100%
This mixture was applied by padding to 70% wet pick up.  The  fabric
was dried at 150F 5 to 10 minutes; pressed at 320F, and cured at
340F for 5 minutes.  It is noteworthy that this treatment contains no
soil-release agent.
The soiling and laundering pf  these  fabrics was  carried  out by both
the Spangler multi-cycle and  the Colgate  single  cycle procedures.  The
detergent in all cases was AATCCWOB  and the water was 200 ppm hardness,
4 Ca:lMg.  In the Spangler tests the  detergent  concentration was  0.3%.
                                 171

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 The Colgate tests, as always, were run as detergency v.  concentra-
 tion series.
      The results of the Spangler tests are shown in Figure 37-39.
 The difference between the green reflectance values and  the white-
 ness indicates that the permanent press treatment tends  to alter the
 hue of the fabric slightly.  This alteration is noticeable to  the eye
 on Dacron but not on cotton.   The slope of the curves in Figures 38
 and 39 indicate that the treatment makes the fabric less prone to
 soil accumulation.  The commercial blend fabric (Figure  39) loses
 whiteness more rapidly than any of the other four fabrics.
      The results of the Colgate tests are diagrammed in  Figures 40-45.
 They show the soil pick up during swatch preparation as  well as the
 washing behavior.  The permanent press finish obviously  makes  cotton
 much more prone to pick up soil than it is in the unfinished state.
 It  also raises the minimum effective concentration (MEG) of the de-
 tergent,  i.e.  the concentration necessary to reach the detergency
 plateau.   Treatment has relatively little effect on the  soil pick
 up  of the  Dacron,  but  it does make the Dacron more difficult to
 clean.   The  blend fabric (Figures 44 and 45)  behaves as  expected
 like  a  mixture of treated Dacron and treated cotton.  The fact that
 the absolute reflectance level of the blend fabric is  higher than that
 of  the  laboratory treated fabrics is ascribed to a different finishing
 treatment.   It is  probable that a soil release ingredient was  in-
 cluded  in  the  treating formula used  on the commercial fabric.
      It  is generally believed among  textile chemists that the  per-
manent press finish  has  little effect  on the  polyester component of
a blend fabric  because  the  aminoplast  prepolymer does  not penetrate
to the fiber interior.   The present  study indicates  that sufficient
final polymer remains adherent  to the  polyester's  surface to change
its soiling and washing  characteristics very  markedly.   The results

                               172

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indicate, in fact,  that this typical  permanent press  finish affects
the polyester fully as much as the cotton with regard soilability
and launderability.
                                173

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                    Table BG1

INSTRUMENTAL REFLECTANCES OF IAUNDERED PILLOWCASES
         AFTER SIX CYCLES IN BUNDLE TEST

AHAM durapress
D durapress
AHAM cotton
D cotton
AHAM durapress
M durapress
AHAM cotton
M cotton
G
83.8
84.0
90.1
90.4
83.3
83.0
88.9
87.6
Delta G
AHAM
0
-0.2
0
-0.3
0
0.3
0
1.3
Whiteness
76.2
76.0
76.5
75.2
71.3
67.8
66.1
59.6
Delta
Whiteness
AHAM
0
0,2
0
1.3
0
3.5
0
6.5
Yellowness
.01
.01
.03
.04>
.02
.03
.06
.08
Delta
Yellowness
AHAM
0
0
0
.01
0
.01
0
.02
                      174

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           Table BG2

TERGOTOMETER SOIL REMOVAL VALUES
    Cotton, 0.2%, Tap Water
Col. 1
Procedure
No..

1
2

1
2

1
2
2
3 | 4
Delta Values Reflectance
vs AHAM
G

3.10
-.20

l.AO
-1.60

.60
0
Whiteness

1.90
-.50

.60
-.80

.10
0
Yellowness
Detergent
D
.003
.002
Detergent
M
.003
-.002
Detergent
AATCC #124
.003
.004
5
.
'
Alcohol Extractable Material
% on soiled
swatches

1.19
7.76

1.19
7.76

1.19
7.76
% on washed
swatches

.75
2.61

1.01
2.68

.56
2. 64
Delta vs
AHAM

-.03
.03

-.29
-.04

.16
0
           175

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           Table BG2A

TERGOTOMETER REDEPOSITION VALUES
    Cotton, 0.2%, Tap Water
Col. 1
Procedure
No.


1
2


1
2

1
2
2
3
4
Delta Values Reflectance
vs AHAM
G


-5.6
-0.6


-3.8
-0.3

-2.8
-0.7
Whiteness


-5.2
-1.3


-3.2
0.3

-1.5
0.1
Yellowness
Detergent
D
.004
.003
Detergent
M
.002
.Q01
Detergent
AATCC #124
.003
.002
5
, 1 ,
Alcohol Extractable Material '

% on soiled
swatches











% on washed
swatches












Delta vs
AHAM











         176

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           Table BG3

TERGOTOMETER SOIL REMOVAL VALUES
   Durapress, .2%, Tap Water
Col. 1
Procedure
No.


2


2

2
2
3
4
Delta Values Reflectance
vs AHAM
G


11.6


7.80

-1.50
Whiteness


9.6


6.70

-1.30
Yellowness
Detergent
D
.001
Detergent
M
-.001
Detergent
AATCC #124
-.001
5
6
7
Alcohol Extractable Material
% on soiled
swatches


7.37


7.37

7.37
% on washed
swatches


2.35


2.58

1.82
Delta vs
AHAM


-.39


-.62

.14
           177

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           Table BG3A

TERGOTOMETER REDEPOSITION VALUES
   Durapress, 0.2%, Tap Water
Col. 1
Procedure
No.

2

2

2
2
3
4
Delta Values Reflectance
vs AHAM
G

.3

-1.2

-0.3
Whiteness

.4

-0.8

-1.0
Yellowness
Detergent
D
.000
Detergent
M
.000
Detergent
AATCC #124
.004
5
6
7
Alcohol Extractable Material

% on soiled
swatches






% on washed
swatches






Delta vs
AHAM






         178

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           Table BG4

TERGOTOMETER SOIL REMOVAL VALUES
    Cotton, 0.3%, Tap Water
Col. 1
Procedure
No.





3
4
5


3
4
5


3
4
5
2
3
4
Delta Values Reflectance

vs AHAM

G


-.80
-4.40
-4.80


-.90
-3.30
-4.40


-.50
-1.50
-1.70

Whiteness


1.20
-5.00
-4.70


1.90
-3.00
-4.10


1.00
.30
.30

Yellowness
Detergent
D
-.006
.011
.009
Detergent
M
-.010
.006
.007
Detergent
AATCC #124
0
.002
.001
5 | ,
7
Alcohol Extractable Material

% on soiled
swatches
Swatches


4.74
1.44
5.69


4.74
1.44
5.69


4.74
1.44
5.69
% on washed"
swatches
Swatches


3.29
.39
3.39


3.53
.45
3.37


3.07
.61
2.81
Delta vs
AHAM



.91
.18
-1.60


.67
.12
-1.58


-.87
-.04
-1.02
           179

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           Table BG4A

TERGOTOMETER REDEPOSITION VALUES
    Cotton, 0.3%, Tap Water
Col. 1
Procedure
No.






3
4
5


3
4
5


3
4
5
2
3
4
Delta Values Reflectance

vs AHAM

G



-0.5
-1.4
-1.5


-0.4
-1.2
-1.2


-0.6
-1.5
-1.3
Whiteness



-0.3
-2.9
-3.0


-0.3
-2.2
-1.4


1.2
0.7
2.2
Yellovmess
Detergent
D

-.001
.007
.006
Detergent
M
-.001
.006
.001
Detergent
AATCC #124
.001
.002
-.004
5
6
7
Alcohol Extractable Material

% on soiled
swatches

















% on cashed
swatches

'** "
... |..
; I
!












Delta vs
AHAM

















         180

-------
           Table BG5

TERGOTOMETER SOIL REMOVAL VALUES
   Durapress, 0.3%, Tap Water
Col. 1
Procedure
No.





3
4
5


3
4
5


3
4
5
2
3
4
Delta Values Reflectance

vs AHAM

G


3.30
-2.50
-3.20


2.40
-2.80
-3.00


-.10
-.10
-.60.
Whiteness


4.60
-4.40
-4.00


4.30
-4.80
-3.00


-.80
-.50
-1.60
Yellowness
Detergent
D
-.010
.012
.010
Detergent
M
-.010
.013
.006
Detergent
AATCC #124
.002
.002
.006
5
6
7
Alcohol Ext rac table Material

% on soiled! % on washed
swatches 1



4.24
1.88
4.30


4.24
1.88
4.30


4.24
1.88
4.30
swatches



1.97
.65
1.99


1.60
.65
1.84


1.61
.72
1.72
Delta vs
AHAM



-.26
0
-.42


.11
0
-.27


.10
-.07
-.15
         181

-------
           Table BG5A

TERGOTOMETER REDEPOSITION VALUES
   Durapress, 0.3%, Tap Water
Col. 1
Procedure
No.





3
4
5


3
4
5



3

4
5
2
3
4
Delta Values Reflectance

vs AHAM

G


-.1
.3
.4


0
.1

.2



0
-.1
0
Whiteness


1.0
-.8
-1.0


-.4
-.9

-.1



.2
-.5
-.9
Yellowness
Detergent
D
-.003
.004
.005
Detergent
M
.001
.003

.002
Detergent
AATCC #124

0
.001
.003
5
6
7
Alcohol Extractable Material

% on soiled
swatches



















% on washed
swatches


















Delta vs
AHAM


















          182

-------
                      Table BG6



RANKINGS OF DETERGENTS IN DIFFERENT WASHING PROCEDURES




        Whiteness Ranking of Soiled Swatches
Procedure 0.2 % , Tap Water 0.3 %, Tap Water
Cotton DP Cotton
Bundle fAHAM fAHAM
|p |p
M M
i PAHAM
AATCC
X]
DJ
2 fM fAATCC
D LAHAM
AATCC M
.AHAM D
3
PD M
W D
"AHAM
M
AATCC
J>
"AHAM
D
AATCC
J
"AHAM
AATCC"
J)
M
k D
fD fM M
1$ ID fAHAM
LAATCC
5 fD
D fM LM
M to AHAM]
AATCCJ
DP







"AATCC
AHAM
M
JD
fAATCC
LAHAM
Ml
Dj
B
AATCCl
AHAMJ
(3
LAATCC
AHAM
                       183

-------
                                               Table BG7
                      WHITENESS RANKINGS OF SOILED SWATCHES  IN PROCEDURES  1  and 2
Procedure
1
2
0.1 %,
Cotton
AHAM"]
AATCCJ
M
D
M
D
AATCCf]
AHAM J
Tap Water
DP

AATCC
AHAM
Ml
DJ
0.1 %,
Cotton
AATCC"!
AHAM J
M
D
M
AATCC]
D J
AHAM
Hard Water' 0.2 %
Hard Water'
DP , Cotton DP
i
M "|
AATCCj
AHA1VU
AATCC
AHAMl
M J
D
M
AHAM
AATCC
D
!
*
i
i
AATCC] 1
AHAM J !
M i
D i
0.3 %,
Cotton
AATCC "I
AHAM
M J
D
"AHAM
AATCC
M
P
Hard Water
DP

[AATCC
LAHAM
M
D
oo
*>

-------
                          Table BG8

WHITENESS BANKINGS OF SOILED SWATCHES IN PROCEDURES 3, 4 and
                       0.3%; Hard Water
Procedure Cotton
3 AHAM]



"MTCQJ
M
i)
DP
AATCC]
AHAMJ
M
D
                             AHAM")
                             AATCCJ
                             AATCCl
                             AHAMJ
 D
 M
 AATCC]
 AHAMJ


fD
[M
 AATCC]
 AHAMJ
                              185

-------
                                                   Table BG9

                                   WHITENESS RANKINGS OF  SOILED SWATCHES
                                DETERGENTS  M and D  IN PROCEDURES  3,  4 and  5

                          of   Ti^r-v  T.T'-.-f-^v-.     O  T  <~"   T.Tr--w^-1 1,T^(-/-.->-.  C\  O ff
oo
Procedure
3
11
5
U.I 7o, !'
Cotton
CJ
D
M
D
M
ap v.'a^er
DP
M
D
fM
LD
M
D
U.I /i, J:L.
Cotton
fM
LD
P
LM
fM
LD
ra v/arer
DP
M
D
fD
M
D
U.el /o, He
Cotton
p.l
LD
P
LM
P
LM
ira vjare:
DP
M
D
K
M
D
r u.j "f,, tic
Cq>tton
fM
LD
P
LM
P
LM
ira v,!ater
DP
M
D
D
M
P
LM

-------
    WHfTENLSS
             ed_doi!ioii_
              dotlon
OUntrea
4 Tr^ater
             lEFltCTANCi
 GREEN
  Untrea
             ed
              Cotton
20
Figure 37-
                    1                     2

                Number  of soil/wash  cycles

       Fabric finish study.  Spangler multicycle.  200 ppm water,
       AATCCWOB 0.3%.  Cotton.
                       187

-------
Figure 38.
             1                      2

         Number  of soil/wash-cycles

Fabric  finish study.   Spangler multicycle.
200 ppm water.  AATCCWOB 0.3%.  Dacron.
                        188

-------
    WHITENESS
   .iL ' ..
              I   i  i
                       1                     2

                   Number of soil/wash cycles

Figure 39.  Fabric finish study.  Spangler multicycle.
          200 ppm water. AATCCWOB 0.3%.  Blend fabric,

                      189

-------
VO
o
      Before
      Soiling
                               Figture 40.
              .1                      .2
        Detergent concentration  in  bath (%)

Fabric finish study.  Colgate soil.   200 ppm water
AATCCWOB.   Cotton.  Green reflectance values.
.3

-------
                              100
vo
      Before
     Soiling
After
Soiling
Detergent concentration in bath (%)
                              Figure 41.   Fabric finish study.   Colgate soil.  200 ppm water.
                                          AATCCWOB.  Cotton.  Whiteness values.

-------
   (A
   i
o
   c  
   0)
   U
   C  -:
   Q>
     Before
     Soiling
After
Soiling
                         .1                      .2
          	 ,.i- <-- -^ -
                 Detergent concentration in  bath (%)
Figure 42.  Fabric finish study.   Colgate soil.  200 ppm water.
            AATCCWOB.  Dacron.   Green reflectance values.

-------
                              100
VO
(jO
      Before
      Soiling
After
Soiling
                         .1                      .2

                    Detergent  concentration  in bath (%)

Figure 43.   Fabric finish study.  Colgate soil.   200  ppm water.
            AATCCWOB.  Dacron.   Whiteness values.

-------
    U

    (A

    i
i-   U)
vo   *-  	
4>-   '-

    3


    0
    U
    c

    (tf
    +
    U
     Before

     Soiling
After

Soiling
                         .1                      .2


                    Detergent concentration  in  bath (%)


Figure 44.   Fabric finish  study.  Colgate soil.  200 ppm water.

            AATCCWOB.   Blend  fabric  (commercial permanent press  finish).

            Green reflectance values.
                                                                                     .a

-------
     u

     u


     Cfl
     10
     0)
vo
Oi
    tt)
    U
    c
    10
    <
    u
    0)
    or
     Before
     Soiling
After
Soiling
  0                      .1                       .2

                    Detergent concentration  in bath (%)

Figure 45.   Fabric finish study.  Colgate soil.  200 ppm water.
            MTCCWOB.   Blend  fabric  (commercial permanent press  finish)

            Whiteness  values.
.3

-------
   23456
   ML 2% Mquestrant solution added
I.-. Jon  curvi of t/f/Jeal  itrong, htgh efficiency
ch*Jant, ,'i'cA
                       ttlomer,

-------
                 23456
                 ML 2% MquMtrant solution addtd

Figur* 47.  ChfUtion curv of wak, modrat efficiency ch*Unt,
           Na cittaU and
                        197

-------
                                       294-10  nSppm
                 2345
               ML  2%  sequestrant solution added
igure 48.  Low efficiency polymeric chelants.  Akzo 294-10 moderately
          strong, POCNa moderately weak.
                       198

-------
                             TTMW 2SOO) IJLS
         123456
                ML 2% sequestrant solution added

Figure  49.  Effect of molecular weight on chelating behavior in
           polyacrylic acids  (Calnox).  Akzo  OS starch typical of  low
           efficiency moderate strength polymeric builders.

                         199

-------
 Code  No.
                   APPENDIX C

             CODE LIST OF MATERIALS


            Type
     Identity
 20-138     Fatty alcohol ethoxylate  surfactant


 20-141     Polymeric builder


 20-144     Hydroxylated  nonionic  surfactant


 20-145     Hydroxylated  nonionic  surfactant


 20-146     Low titer soap

 20-147     High titer soap
20-151
Glucoheptonic acid builder
20-152     Citric acid  (sodium salt) builder

22-155     Alpha olefin sulfonate surfactant


26-189     Hydroxylated nonionic surfactant



26-191     Hydroxylated nonionic surfactant



31-230     Sucrose Hexadecyl Ether
                                      Plurafac A-38 (Wyan-
                                      dotte Chem. Corp.

                                      Experimental 18507-27
                                      (Celanese Chem. Co.)

                                      Ninol AA62 (Stepan
                                      Chemical Co.)

                                      Nittoester P-1570 (Dai
                                      Nippon Sugar Mfg. Co.)
Seqlene S540  (Pfansti-
ehl Laboratories,  Inc.)

Pfizer Chemicals Div.

Bioterge AS-35-CL
(Stepan Chem. Co.)

Experimental compound
IL728 (Atlas Chem.
Industries, Inc.)

Experimental compound
IL725 (Atlas Chem.
Industries, Inc.)

Experimental compound
1303-23, GRI
                              200

-------
 Appendix  C  (Continued)
 Code No.
            Type
    Identity
 32-237      Commercial detergent extract
 34-249     Alkyl aryl sulfonate  (IAS)
 36-276     Experimental  formulation, GRI
 36-277     Experimental  formulation, GRI
 36-278     Experimental formulation, GRI
 38-279     Diglycollic acid  (Na salt)
 38-282
Commercial detergent
 40-309     Diglycollic acid  (Na salt)
 40-310     Polymeric builder
 40-312     SAND,  Monoacidamide  of  nitrilo-
            triacetic  acid

40-332     Ether carboxylate anionic surfac-
           tant

42-348     Sulfo zwitterionic surfactant
42-350     Sulfobetaine zwitterionic surfac-
           tant
Alcohol soluble mate-
rial (surfactant) ex-
tracted from Tide XK

Ultrawet K Special
(Arco Chem. Co,)
                 *
40 Hi titer soap/15 Al-
fonic 1218-60/8G/1/36

40 Low titer soap/15
Alfonic 1218-60/8G/1/36

20 Low titer soap/15
Alfonic 1218-60/8G/1/
36/+20 H20

Biosoft SB-1
(Stepan Chem. Co.>
                t
Concern (H.T.Develop-
ment , Inc.)
Purchased 1970

Experimental compound
SN1048 (Celanese
Chem. Co.)

Gantrex AN-119
(GAF Corp.)

(Bethlehem Steel Co.)
                                     Experimental  compound
                                     1245  (Dow  Chem.  Co.)

                                     Sulfobetaine  DLM
                                     (Textilana Corp.)

                                     Sulfobetaine  TA75
                                     (Textilana Corp.')
                              201

-------
Appendix C  (Continued)
Code No.
Type
                                                   '  Identity
42-353


43-64


43-65


43-67


43-74

43-83
46-356


46-357


48-374


51-91


51-93


51-100


51-101
           Sulfo zwitterionic surfactant


           Commercial detergent, high carbon-
           ate type.

           Polymeric builder
           Fatty alcohol ethoxylate surfac-
           tant
           Polymeric builder
           Hydroxylated nonionic surfactant
           Carboxy zwitterionic surfactant
           Carboxy zwitterionic surfactant
           Amine oxide surfactant
           Alkane sulfonate anionic surfac-
           tant

           Fatty alcohol ethoxylate nonionic
           surfactant

           Fatty alcohol ethoxylate nonionic
           surfactant

           Fatty alcohol ethoxylate nonionic
           surfactant
                          Sulfobetaine DP
                          (Textilana Corp.)

                          Sears Laundry Deter-
                          gent - Phosphate  Free

                          Versicol E7 (Allied
                          Colloid Mfg. Co.)

                          Arosurf 63PE16 (Ash-
                          land Chemical Co.)
                          Experimental 18507-48
                          (Celanese Chem. Co.)

                          Experimental surfac-
                          tant 31-43 (Northern
                          Regional Laboratory
                          USDA)

                          Velvetex BC (Textilana
                          Corp.)

                          Tegobetaine C (Gold-
                          schmidt Chemical  Div.)

                          Aromox C/12W (Armour
                          Industrial Chem.  Co.)

                          Hostapur SAS-60
                          (American Hoechst Corp.)

                          Alfonic 1618-65
                          (Continental Oil  Co.)

                          Arosurf 63-E15
                          (Ashland Chem. Co.)

                          Arosurf 42-E12
                          (Ashland Chem. Co.)
                               202

-------
Appendix C  (Continued)
 Code No.
Type
Identity
 51-104     Fatty alcohol ethoxylate nonionic
           surfactant

 51-105     Fatty alcohol ethoxylate nonionic
           surfactant

 54-431     Sulfo zwitterionic surfactant
 54-433      Sulfo zwitterionic surfactant


56-445     Hydroxyethylimino diacetic acid

58-466     Polymeric builder


58-467     Polymeric builder


58-471     Ether sulfate anionic surfactant
60-486     Ether carboxylate anionic surfac-
           tant

62-491     Ether sulfate anionic surfactant
62-492     Ether sulfate anionic surfactant
66-530     Carbohydrate type polymeric builder
66-532     Polymeric builder
                          Plurafac B-26
                          (Wyandotte Chem. Co.)

                          Plurafac D-25
                          (Wvandotte Chem. Co.)

                          Miranol CS Cone.
                          (Miranol Chem. Co.)

                          Miranol DS
                          (Miranol Chem. Co.)

                          (Bethlehem Steel Co.)

                          Experimental  Product
                          335  (Amicon Corp.)

                          Experimental  Product
                          933  (Amicon Corp.)

                          Steol 4N (Stepan
                          Chem. Co.)

                          Experimental  compound
                          7-26A (Dow Chem.  Co.)

                          Alfonic  1412-5 (Con-
                          tinental Oil  Co.)

                          Experimental  compound
                          1218-EO-50-S  (Con-
                          tinental Oil  Co.)

                          Dicarboxyl starch
                          (fever Bros.)

                          Experimental  deter-
                          gent builder  S-10244-
                          137-1  (American Cya-
                          namid Co.)
                               203

-------
Appendix C (Continued)
 Code No.
             Type
     Identity
 66-533
 66-541
 68-108
 68-109
 68-127
 68-134
 68-558
70-560
72-589


74-594
 Polymeric builder
 Monomeric builder,  carboxylic acid
 type
 Sulfo ampholytic surfactant
 U.S.  Patent 3,084,187

 Sulfo ampholytic surfactant
 U.S.  Patent 3,084,187

 Fatty alcohol  ethoxylate  nonionic
 surfactant

 Fatty alcohol  ethoxylate  nonionic
 surfactant

 Alpha olefin sulfonate anionic
 surfactant
Commercial detergent
Monomeric builder
Soap type surfactant
74-596
Monomeric builder
 Experimental detergent
 builder S-10244-137-2
 (American Cyanamid Co.)

 Experimental compound
 SN1152 (Celanese
 Chemical Co.)
             t
 GRI experimental com-
 pound #1303-6 (GRI)

 GRI experimental com-
 pound #1303-7 (GRI)

 Alfonic 1218-60 (Con-
 tinental Oil Co.)

 Neodol 25-7 (Shell
 Oil Co.)

 Experimental compound
 OLS07 (Gulf Research
 and Dev.  Co.)

 Amway "L.O.C."  Liquid
 Organic Concentrate
(Ataway Corp.)
 Purchased 1971

 Monoethanolamine
 Carbonate (GRI)

 #544-151A Soap/lime
 soap  dispersing  agent/
 builder (Eastern Uti-
 lization  Research  &
 Dev.  Div.  USDARS)

 DL-tartaric acid
 (Aldrich  Chem. Co.)
                             204

-------
Appendix C (Continued)
Code No.
            Type
    Identity
74-602
74-604


74-606


76-620



,78-633

78-634


78-635


80-647


86-700
86-704


86-705
Carbohydrate type polymeric builder
Alpha olefin sulfonate anionic
surfactant

Monomeric builder
Monomeric builder



Ether carboxylate surfactant

Ether carboxylate surfactant
Fatty alkyl sulfate anionic surfac-
tant

Monomeric builder
Laundry Detergent
Carbohydrate builder
Unidentified carboxylated polymer
Carboxymethyl starch
(Northern Regioaal Re-
search Laboratories
USDA)

Bioterge AS40G (Stepan
Chemical Co.)

Mellitic acid (Chem.
Procurement Laboratories)

Tetrahydrofuran-2,3,4,
5-tetracarboxylic acid
(Aldrich Chemical Co.)

Sandopan DTC (Sandoz)

Sandopan DTC 100
(Sandoz)

Dupanol ME Dry
(Dupont Co.)

Carboxymethyl oxysuc-
cinic Acid

Standard Laundry De-
tergent AATCCWOB from
Am. Assoc. Textile
Chemists & Colorists

Methocel XDL 7823
(Dow Chemical Co.)

Polyelectrolyte
NX524  (Nalco Chem.Co.)
                               205

-------
Appendix C  (Continued)
Code No.
            Type
     Identity
86-706
 Soap type surfactant
86-707
88-723
88-726
Soap type surfactant
86-708     Soap type surfactant
86-709     Maleic copolymer builder
88-722     Laundry detergent
Laundry detergent
Laundry detergent
 ER AF569-144-1  Soap/
 lime  soap  dispersing
 agent builder  (Eastern
 Utilization Research
 and Dev. Div. USDARS)

 ER AF569-144-2  Soap/
 lime  soap  dispersing
 agent builder  (Eastern
 Utilization Research
 and Dev. Div. USDARS)

 ER AF569-144-3  Soap/
 lime  soap  dispersing
 agent builder  (Eastern
 Utilization Research
 and Dev. Div. USDARS)

 Experimental compound
 Maldene 270 (Borg-
 Worner Co.)

 Commercial laundry de-
 tergent, purchased
 Chicago, 111. 1972
 Breeze (Lever Bros.)

 Commercial laundry de-
 tergent, purchased
 Chicago, 111. 1972
 Wisk  (Lever  Bros.)

 Commercial laundry de-
 tergent , purchased
 Chicago, 111. 1972
Ajax  (Colgate-Palmol-
 ive Co.)
                             206

-------
Appendix  G  (Continued)
 Code  No.
            Type
     Identity
 90-727
Laundry detergent
 90-729
94-760
96-782
96-783
96-784
98-806
Laundry detergent
 90-730     Anionic sulfonate surfactant
92-745     Acrylic builder
92-752     Alkyl aryl sulfonate (LAS)
Laundry detergent
Laundry detergent
Laundry detergent
Unidentified Polymeric builder
 Commercial  laundry de-
 tergent  purchased
 Chicago  1972  --  Cold
 Power  (Colgate-Palmol-
 ive  Co.)

 Commercial  laundry de-
 tergent  Opus  (Fenom
 Corp., Goteborg, Sweden)

 Chevron  D116  (Standard
 Oil  Co.  of  California)

 Goodrite K732 (B.F.Good-
 rich Chem.  Co.)

 Conoco C550 (Continen-
 tal  Oil  Co.)

Bioterge TMS
 (Stepan Chemical Co.)
 Commercial  laundry de-
 tergent  - purchased
 1973 Era (Proctor &
 Gamble Co.)

 Commercial  laundry de-
 tergent  purchased
 Miami, Fla.  1973--
 Cold Power  (Colgate-
 Palmolive Co.)

 Commercial  laundry de-
 tergent  purchased
 Miami  1973Tide
 (Proctor &  Gamble)

 Experimental compound
 IL 740 (Atlas Chem.
 Indus tries, Inc.)
                               207

-------
Appendix C  (Continued)
Code No.
            Type
    Identity
98-807
Unidentified polymeric builder
100-821    Unidentified polymeric builder
100-822    Carboxylated starch
100-823    Acrylic builder
100-824    Acrylic builder
102-833    Carboxyethyl Acetone
102-834    Carboxylated starch builder
102-836    Fatty acid diethanolamide
           condensate surfactant

104-855    Laundry detergent
Experimental compound
IL741  (Atlas Chem'.
Industries, Inc.)

Experimental compound
XL,759 (Atlas-Chem.
Indus trie s, Inc.)

Experimental cpmppund
OS starch (Akzo Huishou-
delijke Produkten NV,
The Hague, Holland)

Experimental compound
CaInox 214DN (Aquanes s
Chem. Co.)

Experimental compound
Calnox 231 (Aquaness
Chem. Co.)

GRI experimental com-
pound prepared accord-
ing to U.S. Patent
3,716,487

Experimental compound
starch 294-10 (Akzo
Huishoudelijke Pro-
dukten NV, The Hague,
Holland)

Superamide L9A
                                      Commercial laundry de-
                                      tergent - purchased
                                      Washington, D.C.-1973
                                      Dynamo (Colgate-
                                      Palmolive Co.)
                               208

-------
Appendix C (Continued)
Code No.
Type
Identity
104-856    Sodium dodecylbenzene
           sulfonamodiethyl sulfate sur-
           factant

104-.860    Hydroxylated acrylic
           copolymer builder

106-866    Maleio telomer builder
106-871    Maleic homopolymer builder
108-880    Sulfopropionate surfactant
                          ER AF594-37 (Eastern
                          Utilization Research
                          & Dev. Div. USDARS)

                          Experimental compound
                          POCNA (DEGUSSA)

                          6RI experimental com-
                          pound

                          6RI experimental com-
                          pound

                          ER AFP610-007  (Eastern
                          Utilization Research &
                          Dev. Div. USDARS)
                               209

-------
                              APPENDIX D
Selected Recent Patents Relating to Phosphate-Free Household Laundering
Detergents                                      '


A.   Monomeric Builders

     1.   C.A., 22 (1972) 154319n N,N-Bis (phyroxyethyl) - substituted
          amino acids as builders for detergents.  Rempfer, Heinz;
          Grossman, Heinrich (Chemische Werke Huels A.-G.) Ger. Offen.
          2,103,725, 10 August 1972, 7 pp.

     2.   C.A., 7 (1973) 60055s N-Substituted disodium aminodicarboxy-
          lates as builders for detergents.  Rempfer, Heinz (Chemische
          Werke Huels A.-G.) Ger. Offen. 2,125,249, 30 November 1972,
          11 pp.
               N-substituted aspartates and iminodiacetates.

     3.   C.A., 77. (1972) 138233v Phosphate-free detergent composi-
          tions.  Kusashio, Koji; Ninagawa, Sadayoshi (Ajinomoto Co.,
          Inc.) Japan Kokai 72 16,504, 2 September 1972, 5 pp.
               Glutatnates and aspartates.

     4.   C.A., 7]_ (1972) 138238a Detergent formulations containing
          nonphosphorus builders.  Yang, Meiling T. (Ethyl Corp.)
          U.S. 3,717,591, 20 February 1973, 6 pp.
               Sulfoethylimino diacetic acid.

     5.   C.A., Ji (1972) 142706c Detergent formulations containing
          water-soluble salts of N,N-bis(carboxymathyl)aspartic acid
          as builders.   Yang,  Meiling T. (Ethyl Corp.) U.S.
          3,637,511,  25 January 1972,  5 pp.

     6.   C.A.,  26 (1972) 129230y Detergent formulations containing
          nonphosphorus builders.   Yang, Meiling T. (Ethyl Corp.)
          U.S.  3,635,829, 18 January 1972,  5 pp.
               Sulfopropylimino diacetic acid.

     7.    C.A.,  78 (1973) 5729q Iminodisuccinic acid salts as deter-
          gent  builders.   Tate,  Bryce  E.; Berg, Rudolph G. (Pfizer Inc.)
          U.S.  3,697,453,  10 October 1972,  4 pp.
                              210

-------
 8.   C.A.,  21 (1972)  154302b Detergent.   Unilever N.V.  Neth.
      Appl.  72 00,084,  07 July 1972,  13 pp.
           Pyridine dicarboxylic acid.

 9.   C.A.,  7.7 (1972)  126134a Sulfonated alkanedicarboxylate
      builders for detergents.  Von Praun, Ferdinand; Amende,
      Joachim (Chemische Werke Huels A.-G.)  Ger.  Offen.  2,143,010,
      01 March 1973, 19 pp.
           Sulfonated adipic acid and homologs.

10,   C.A.,  J2 (1972)  138234w Sequestering agents and detergent
      builders.   Lannert, Kent Philip (Monsanto Co.) Ger.
      Offen. 2,231,927, 18 January 1973,  21 pp.
           2-oxa-l,3,3  butane tricarboxylic acid and analogs.

11.   C.A,,  78 (1973)  99507r tf- Substituted-p -sulfosuccinic acids
      as detergent builders.  Lamberti, Vincent (Unilever N.V.)
      Ger. Offen. 2,230,073, 28 December 1972, 37 pp.
           ahydrbxy - B sulfosuccinic acid and analogs.

12.   C.A.,  2?_ (1973)  113083h Phosphate-free detergents.
      Hentschel,  Gerhard Oskar (Hentschel, Valter S.E.)  Ger.
      Offen. 2,228,252, 21 December 1972, 12 pp.
           monopropyl ester of malic acid

13.   C.A.,  78. (1973)  45433v Detergent builders.   Konort, Mark D.;
      Lamberti,  Vincent; Weil, Ira (Unilever N.V.) Ger.  Offen.
      2,220,295,  16 November 1972, 39 pp.
           Carboxyalkyl substituted malic and aspartic acids.

14.   U.S. Patent 3,692,685 Detergent cooipositions.
      Vincent Lamberti, Mark D. Konort and Ira Weil to Lever
      Brothers Company, September 18, 1972.
           Carboxymethyloxysuccinic acid (CMOS).

15.   C.A.,  78, (1973) 45417t Detergent formulations.
      Lannert, Kent P.  (Monsanto Co.) U.S. 3,704,320, 28 November
      1972,  2 pp.
           2,4-dioxapentane-1,3,3,5-tetracarboxylic acid.

16.   C.A.,  77 (1972) 11639y Enzymic detergents containing ci-
      trate builders.  Mast, Roy Clark (Proctor and Gamble Co.)
      Ger. Offen. 2,161,779, 29 Jun 1972, U.S. Appl. 98,114,
      14 December 1970; 40 pp.
                           211

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 17.  C.A.,  77  (1972)  166522m Built detergent  formulations.
     Harken, Russell  D.  (Monsanto Co.) U.S. 3,689,418,
     05  September  1972,  2 pp.
          Ethenetetracarboxylic acid.

 18.  Dutch  Pat. Appl'n   70-17181, 24 November  1970,
     D.  S.  Conner  and J. E. Thompson to the Proctor and Gamble  Co.
     Built  Detergent  Composition.  Corresponds to Belg. Pat.
     759,283 and U.S. Serial No. 879,612.
          Mellitic Acid.

 19.  C.A.,  21  (1972)  116399 Detergent builders.
     Benjamin, Lawrence; Connor, Daniel Stedman  (Proctor and
     Gamble Co.) Ger. Offen. 2,161,768, 06 July  1972, 41 pp.
          Mellitic acid used with carbonate and  silicate.

 20.  U.S. Patent 3,661,787 Saturated Aliphatic Dicarboxylic Acid
     Salts  as Detergent Builders, George E. Brown, Jr. to the
     Pollutrol Group, May 9, 1972.
          Succinic and oxalic acids.  Claims limited to potas-
          sium palmitate as the surfactant.

 21.  C.A.,  21  (1972)  50565y Detergent builders.  Lamberti, Vincent
     (Unilever N.V.)  Ger. Offen. 2,150,544, 13 April 1972, 15 pp.
          Oxydiacetic acid.

 22.  C.A.,  21  (1971)  111128r Phosphate-free builders for deter-
     gents.  Konort, Mark D.; Lamberti, Vincent  (Unilever N.V.)
     Ger. Offen. 2,057,259, 09 June 1971, 17 pp.
          Tetrahydrofuran tetracarboxylic acid.

 23.  C.A., 28  (1973)  5720e Tetrasodium tetrahydrofurantetra-
     carboxylate builder for detergents.  Jakobi, Guenter;
     Perner, Johannes (Henkel und Cie.  G.m.b.H) Ger. Offen.
     2,113,730, 28 September 1972, 29 pp.

 24.  U.S. Patent 3,580,852 Detergent formulations containing
     Tetrahydrofuran 2,3,4,5 - Tetracarboxylic Acid Salts as
     Builders.   Meiling T. Yang to Ethyl Corporation,  May 25, 1971,

25.  U. S. Patent 3,699,159 l,3,5-Trihydroxy-2,4,6-benzene tri-
     carboxylic acid and water soluble salts thereof.
     Daniel S.  Conner and Harry Karl Krummel to the Proctor and
     Gamble Company,  October 17,  1972.
                          212

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26.  C.A., 77 (1972) 128512a Phenolic calcium-complexing agents
     for detergents.  Conner, Daniel Steadman;  Krummel,  Harry Karl
     (Procter and Gamble Co.) Ger.  Offen.  2,164,872,  20  July 1972.
          l,3,5-trisulfo-2,4,6-trihydroxy benzene and 1,3,5-tri-
          carboxy-2,4,6-trihydroxy benzene.

27.  C.A., 77 (1972) 128511z Tetracarboxylie acid detergents.
     Cummins, Richard Williamson; Lancelot,  Charles Julian
     (FMC Corp.) Ger. Offen. 2,165,773 20 July 1972,  26  pp.
          Ethane tetracarboxylic acid and butane-1,2,3,4-tetra-
          carboxylic acid.  Stated to be biodegradable.

28.  U.S. Patent 3,635,830 Detergent compositions containing
     oxydisuccinic acid salts as builders.  Vincent Lamberti and
     Mark D. Konort to Lever Brothers Company,  January 18, 1972.

29.  Ger. Offen. 1,926,422 M. D. Konort and V.  Lamberti  to Uni-
     lever N.V., 4 December 1969, Detergent compositions.  Corre-
     sponds to Fr. Application 2,009,946.
          Oxydisuccinic acid.

30.  U. S. Patent 3,686,124 Carboxymethylated derivates  of di- and
     tri-saccharide compounds and detergent compositions contain-
     ing them.  Warren I. Lyness and James E. Thompson to the
     Proctor and Gamble Co., August 22, 1972.
          Carboxymethylated sucrose, lactose, and raffinose.

31.  U.S. Patent 3,669,890 Builders for synthetic detergent com-
     positions based on carboxyethyl derivatives of polyalcohols.
     Martin M. Tessler and Morton W. Rutenberg to National Starch
     and Chemical Corporation, June 13, 1972.
          Carboxyethyl pentaeryfchritol.

32.  U.S. Patent 3,725,290 Oxyacetic acid compounds as builders
     for detergent compositions.  Douglas Carlyle Nelson and
     Edward Andrew Knaggs to Step an Chemical Company, April 3,
     1973.
          Carboxymethyl ethers of tri- and tetraglyeols,
          pentaerythritol, etc.

33.  C.A., 22. (1972) 77086e Builders for synthetic detergent com-
     positions based on carboxyethyl derivatives of polyalcohols.
     Tessler, Martin M.;  Rutenberg, Morton W.  (National Starch
     and Chemical Corp.)  U.S. 3,669,890, 13 June 1972, 5 pp.
          Carboxyethyl ethers of pentaerythritol and gluconic acid.
                          213

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 34.   C.A.,  76  (1973)  113105s  Sulfosuccinate  salt-containing der
      tergents.  Rempfer, Heinz;  Schulze,  Klaus  (Chemische Werke
      Huels  A.-G.)  Ger. Offen.  2,136,360,  01  February,  1973,  11 pp.
          Sulfosuccinic esters of  fatty alcohol  ethoxylates
          (surface active) used  as builders  for  alkylbenzene
          sulfonates.

 35.   U.S. Patent 3,725,286 Detergent  compositions.
      Robert Pettigrew to Lever Brothers Company, April 3, 1973.
          Long chain succinic  or malonic  acids  (surface active)
          used as  builders for alkylbenzene  sulfonates.

 36.   C.A.,  _78  (1973) 73947J Laundry detergent.   Unilever N.V.,
      Fr. 2,107,437, 09 June 1972,  10  pp.
          Alpha sulfonated fatty acids  as builders.

 37.   C.A.,  72  (1972) 22028g Solid and liquid detergent compo-
      sitions.  Davies, James Francis; Gauterin,  Charles R.;
      Ailbert, Philip A.; Griffiths, Storer C.C.;         J*
      Griffiths, David W. L. (Unilever N.V.)  Ger. Offen.  2,144,592,
      16 March 1972, 12 pp.
          Alpha sulfonated fatty acids  used  as builders for
          anionics or nonionics.

 38.   C.A., 2Z (1972) 116400z Textile  detergents.
      Davies, James Francis; Gauterin, Charles Rowland;
      Griffiths, David W. L.; Storer,  Christopher Charles (Unilever
      N.V.)  Ger. Offen. 2,161,726, 06  July 1972,  21 pp.
          asulfonated fatty acids  (surface active) used as
          builders for alkylbenzene sulfonate.

 39.   C.A., 2 (1973) 113088p Phosphate-free  detergents.
      Pettigrew, Robert; Tissington, Peter (Unilever N.V.)
      Ger. Offen. 2,232,414, 25 January  1973, 11 pp.
          Sodium 2-hydroxy-n-tetradecanoate  used as builder
          for alkylbenzene sulfonate.

40.   C.A., 21 (1973) 31848x Laundry detergent.
     Davies, James Francis; Gilbert, Philip Alan,
      Thompson,  Laurence (Unilever N.V.) Ger. Offen. 2,222,993,
      16 November 1972, 23 pp.  Corresponds to Belg. Patent
      783,176.
          Long  chain alkane 1,2-disulfonates or 1,2-sulfonate-
          sulfinate (surface active) used as builders  for
          alkylbenzene sulfonate.

                          214

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     41.  C.A., 72. (1970) 14116r Taurine derivatives for replacing
          sodium tripolyphosphate in detergents.   Lincoln,  Robert M.;
          Meyers, Joseph Andrew, III; Sauer,  Richard W.  (Atlantic
          Richfield Co.) Fr. 1,556,816,   07 February 1969,  8 pp.
          Corresponds to U.S.  3,579,457,  May 18,  1971.
               Long chain taurine derivatives (surface active) used
               with carbonate  as builders for alkylbenzene  sulfonate.
B.   Polymeric Builders

      1.  U.S. Patent 3,308,067.  Detergent compositions.
          Francis L. Diehl to Proctor and Gamble Co., March 7, 1967,
          11 pp.
               Describes a range of polymeric aliphatic carboxylic
               acids.  Homopolymers and copolymers of acrylic, maleic
               and itaconic acids used as builders for sulfonated or
               sulfated surfactants.

      2.  C.A., 21 (1972) 138227W (Alkyl)cyclopentene-maleic anhy-
          dride copolymer salt builder for detergents.  Tsukuni, Hajime;
          Fujiki, Shun; Tsunoda, Teruo; Ooba, Yoichi (Hitachi Chemical
          Co., Ltd.), Ger. Offen. 2,238,275,  15 February 1973, 19 pp.

      3.  C.A., 78 (1973) 86336j Biodegradable builders for deter-
          gents.  Kramer, J. K.  (Shell Internationale Research
          Maatschappij N. V.) Neth. Appl. 72 05,685, 31 October 1972,
          26 pp.
               Telomers of maleic acid.  Methylisobutyl ketone and
               other materials as telogens.

      4.  C.A., 72 (1972) 154318m Composite maleic anhydride-vinyl
          methyl ether copolymer builders for detergents.
          Grifo, Richard Anthony (GAF Corp.) Ger. Offen. 2,200,779,
          20 July 1972, 21 pp.

      5.  C.A., 2 (1973) 86308b New substitute for  pplyphosphate in
          detergents.  Lauhus, Guenter P. (GAF G.m.b.H., Hamburg, Ger.).
          Seifen, Oele, Fette, Wachse 1972, 98 (26), 869-75  (Ger.)
               Copolymer maleic-methylvinyl ether.

      6.  C.A., 72 (1970) 33192d Textile detergent compositions.
          Arthur, Ralph P.; Belden, M. Joanne (Borg-Warner Corp.)
          Ger. Offen. 1,920,850, 20 November 1969, 14 pp.
               Maleic-butadiene copolymer.
                               215

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 7.  C.A., 7_6 (1972) 74086y Polyelectroylte materials for use
     in detergents.  Lancelot, Charles J.; Mackellar, Donald G.
     (FMC Corp.) Ger. Offen. 2,120,907, 11 November 1971, 26 pp.
          Carbon monoxide-maleic copolymer.

 8.  C.A., 74 (1971) 77660a Poly (maleic acid) and salts for use
     as detergent builders and surfactants.  Bluraberg, John H.;
     MacKellar,  Donald G. (FMC Corp.) U.S. 3,557,065, 19 January
     1971, 3 pp.
          Light-colored sodium polymaleate.

 9.  C.A., 2 (1972) 129218a Sodium polymaleate.
     Blumberg, John H.; Finley, Joseph H.; Rizzo, John J. (FMC
     Corp.) U.S. 3,637,609, 25 January 1972, 3 ?p.
          Refers to a bleached white sodium polymaleate.

10.  C.A., 77 (1972) 90407e Sulfonated copolymers as detergent
     builders.  Westernacher, Helmut; Schulze, Klaus (Chemische
     Werke Huels A.-G.) Ger. Offen. 2,056,813  25 May 1972, 15 pp.
          Sulfonated ethylene-maleic copolymer.

11.  C.A., J76 (1972) 74089b Sulfonated poly (maleic acid) deter-
     gent builders.  Blumberg, John H.; Rizzo, John J.;
     MacKellar,  Donald G. (FMC Corp.) U.S. 3,624,048 30 November
     1971, 4 pp.

12.  U.S. Patent 3,676,373 Detergent Compositions.
     Stanley C.  Paviak to Gulf Research & Development Company,
     11 July 1972.
          Styrene-maleic copolymer of mol. wt. at least 3000.

13.  U.S. Patent 3,730,913 Synthetic detergent compositions.
     Yoichi Oba, Chiharu Kato, Teruo Tsunoda,  and Hajime Tsukuni,
     assignors to Hitachi, Ltd.,  and Hitachi Chemical Company,
     Ltd., May 1, 1973.
          Copolymer of 3a,4,5,6,7,7a-hexahydro-4,7-methanoin-
          dene and maleic anhydride.

14.  C.A., 21 (1972) 138247c Detergent compositions containing
     poly-electrolyte builders.  Tokiwa,  Fumikatsu; Imamura,
     Tetsuya (Kao Soap Co.,  Ltd.) Japan,  Kokai 73,12,807,
     17 February 1973,  5 pp.
          C_ .  alkene-maleic copolymer.   e.g. octene-maleic.
                        216

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15.  C.A., 77 (1972) 141726t Cleaning and soil-preventive com-
     positions.   Schomburg, Noel L., (Monsanto Co.) U. S.
     3,679,592,  25 July 1972, 2 pp.
          Maleic-ethylene copolymer half butyl ester.

16.  C.A., 7_6_ (1972) 115211f Detergent compositions.
     Arthur, Ralph P.; Belden, M. Joanne (Borg-Warner Corp.)
     Ger. Offen. 2,125,461, 02 December 1971, 22 pp.
          Maleic-butadiene copolymer.

17.  C.A., 2 (1973) 60040h Detergent polyelectrolyte builders.
     Martin, Preston Kuhn; Kelly, Richard Howard (Celanese Corp.)
     U.S. 3,706,672, 19 December 1972, 6 pp.
          Polyacrylic acid of controlled mol. wt.

18.  C.A., 2 (1973) 45424t Partial salts of polymerized ali-
     phatic carboxylic acids, for use in detergents.  Unilever N.V.
     Fr. 2,075,287, 12 November 1971, 18 pp.
          Polyacrylic acid.

19.  U.S. Patent 3,692,704 Method of Laundering Fabrics.
     James K. Stamm, Edwin R. Loder, Charles A. Brungs, and
     Herman Kerst to Chemed Corporation, September 19, 1972.
          Mixture of polyacrylic acid and poly
          (N,N-dicarboxymethyl acrylamide).

20.  C.A., 2 (1973) 113104r Sodium poly (a - hydroxyacrylate)-
     containing detergents.  Wegemund, Bernd; Jakobi, Guenter
     (Henkel und Cie.  G.m.b.H.) Ger. Offen. 2,136,672,
     01 February 1973, 34 pp.

21.  C.A., 2 (1973) 99517u Detergents and bleaches containing
     dispersible complex-forming mixtures.  Batka, Heimold;
     Altenschoepfer, Theodor (Henkel und Cie. G.m.b.H.)
     Ger. Offen. 2,134,695, 25 January 1973, 28 pp.
          Aerolein-aerylie copolymer.

22.  C.A., 2 (1973) 99475d Poly (hydroxycarboxylates), a class
     of multiply applicable complexing agents.  Haschke, Heinz;
     Morlock, Gerhard; Kuzel, Peter (Bereich Forsch. Chem.,
     Degussa, Frankfurt/M., Ger.).  Chem.-Ztg. 1972, 96(4),
     199-207 (Ger).
          The properties of the title compds., prepd. from  salts
          of aerolein-aerylie acid copolymer by the Cannizzaro,
          reaction are described with respect to their application.
                          217

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     23.  French Patent 2,083,006.  Product for washing.  Degussa.
          December  10, 1971.
               Acrolein-acrylic acid copolymer converted by Cannizaro
               reaction to allyl alcohol-acrylic copolymer.

     24.  U.S. Patent 3,629,121 Carboxylated starches as detergent
          builders.  Ibrahim A. Eldib, December 21, 1971.

     25.  C.A., _78  (1973) 5672r Dicarboxy group-containing starch
          for detergents.  Powers, Peter James; Reynolds, John Henry
          (Unilever N. V.) Ger. Offen. 2,213,955, 28 September 1972,
          19 pp.
               Purified by treatment with sodium borohydride.

     26.  C.A., 75  (1971) 7765k Detergent composition.  Unilever N.V.
          Neth. Appl. 70 12,380, 23 February 1971, 41 pp.
               Carboxylated starches and celluloses.

     27.  C.A., 72  (1972) 166520J Dicarboxymethyl starch detergent
          compositions.  Cornelissens, Emery G. P.; Ploumen, Jan J. H.
          (Akzo G.m.b.H.) Ger. Offen. 2,207,917, 31 August 1972,
          Neth. Appl. 71 02,556, 25 February 1971, 12 pp.
               Dicarboxymethyl starch.

     28.  U.S. Patent 3,723,322 Detergent compositions containing
          Carboxylated polysaccharide builders.  Francis L. Diehl to
          The Procter & Gamble Company, March 27, 1973.
               Carboxylated alginic acid.
                                                            A
     29.  Starch-derived polyelectrolytes as builders in heavy duty
          detergent formulations.  C. A. Wilham, T. A. McGuire,
          A. M. Mark and C. L. Mehltretter, J. Am. Oil Chemists Soc. 47.
          No. 12,522 (1970).
C.   Surfactants stated to perform well without builders:

      1.  U.S. Patent 3,714,076.  R. G. Anderson to Chevron Research
          Company, 30 January 1973.
               Viscinal disulfates.               '          '-

      2.  U.S. Patent 3,686,098 Novel detergent cdmpositioii;  Ira Weil
          to Lever Brothers Company, August 22, 1972.
               Di-anionic sulfates and sulfonates.
                              218

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 3.   C.A.,  7_6 (1972)  87551w Heavy-duty laundry detergents  con-
     taining polysulfonated alkyl phenols.  Sharman,  Samuel  H.;
     Danzik, Mitchell (Chevron Research Co.)  Ger.  Offen.
     2,121,675,  25 November 1971, 27  pp.

 4.   C.A.,  77 (1972)  77078d 2,2-Disulfonated  dialkyl sulfoxides
     and sulfones.  Nooi,  Jacobus Roelof (Lever Brothers  Co.)
     U.S. 3,666,796,  30 May 1972, 5 pp.

 5.   C.A.,  77 (1972)  63801x Alkyl alkoxybenzene disulfonates.
     Woo, Gar Lok (Chevron Research Co.)  U.S. 3,663,609,
     16 May 1972, 3 pp.

 6.   U.S. Patent 3,707,352 Linear Alkyl Hydrocarbyloxybenzene
     disulfonates.  Gar Lok Woo to Chevron Research Company,
     December 26,1972.

 7.   U.S. Patent 3,697,573 Linear alkylphenol sulfate-sulfonate
     phosphate-free detergent actives.  Mitchell Danzik and
     Ralph House to Chevron Research Company, October 10,  1972.

 8.   Belg.  Appl'n 774,270.  Detergent disulfates of 2-hydrocarbon
     substituted butane diols.  Anderson and  Woo to Chevron Re-
     search Company,  9  January 1970.

 9.   C.A.,  7_8 (1973)  126125y l-(Sulfoalkyl)-4-undecylpyridinium
     inner salts as active detergents.  Roberts, David William
     (Unilever N. V.) Ger. Offen. 2,238,371,  15 February 1973,
     10 pp.
          Zwitterionic  sulfonate.

10.   C.A.,  7B. (1973)  60038p  [(Alkylphenyl)dimethylammonio] pro-
     panesulfonates.   Crabtree, Peter William; Vipond, Peter
     Wilfred (Unilever N.  V.) Ger. Offen. 2,221,938, 23 November
     1972,  12 pp.
          Zwitterionic  sulfonate.

11.   C.A.,  7_8 (1973)  73967r Phosphate-free detergents containing
     glycol alkyl carboxymethyl ethers.  Rempfer, Heinz;
     Amende, Joachim; Stache, Helmut; Grossman, Heinrich
     (Chemische Werke Huels A.-G.) Ger. Offen. 2,124,269,
     30 November 1972,  15 pp.
          Polyether carboxylate
                          219

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     12.  C.A., 2 (1973) 45416s Heavy-duty household detergent com-
          position.  Shane, Hugh J. S. (Hart*Chemical Ltd.) Can.
          912,395, 17 October 1972, 24 pp.
               Polyether carboxylate

     13.  C.A., 77 (1972) 166529u Detergent composition.  Arai,
          Haruhiko; Minegishi, Yutaka; Takeuchi, Takeko (Kao Soap Co.,
          Ltd.) Ger. Offen. 2,206,284, 31 August 1972, 17 pp. '
               Polyether carboxylate

     14.  Can. Patent 873,295 Detergent Compositions.  T. P. Matson
          and J. E. Yates to Continental Oil Company, June 15, 1971.
               Ether sulfonates
                              '.-

     15.  U.S. Patent 3,590,001 Phosphate free heavy duty detergent
          formulations.  Robert C. Taylor and Betty J. Wolsky to
          Atlantic Richfield Company, June 29, 1971.
               Taurine salts of alkylbenzene sulfonates.

     16.  U.S. Patent 3,084,187 Substituted aminoalkanesulfonic acids.
          Van R. Gaertner to Monsanto Chemical Company, April 2, 19631
               Amphoteric taurine derivatives.
D.   Soap plus Lime-Soap dispersers:
                    i

      1.  C.A., 76 (1972) 129203s Soap-based detergent formulations.
          I.  Comparison of soap-line soap dispersing agent formula-
          tions with phosphate-built detergents.  Bistline, R. G., Jr.;
          Noble, W. R.; Weil,  J. K.; Linfield, W. M. (East Reg. Res.
          Lab., Philadelphia,  Pa.) J. Amer. Oil Chem. Soc. 1972, 49(1),
          63-9.

      2.  C.A., 78 (1973) 31799g Soap-based detergent formulations.
          IV.  Synthesis and surface active properties of sulfopropyl
          esters of N-substituted iminodiacetic acids.  Micich, T. J.;
          Sucharski, M. K.;  Well, J. K.;  Linfield, W. M. (East Reg.
          Res. Lab., Agric.  Res. Serv.,  Philadelphia, Pa.) J. Amer*
          Oil Chem. Soc. 1972,  49(11), 652-5.

      3.  C.A., 78. (1973) 31798f Soap-based detergent formulations.
          III.  Surface activity of fatty derivatives of 3-hydroxy-
          propane-sulfonic acid.  Parris, N.;  Weil, J. K.;
          Linfield, W.  M. (East Reg. Res. Lab., Agric. Res. Serv.,
          Philadelphia, Pa.) J. Amer. Oil Chem. Soc. 1972, 49(11),
          649-51.

                               220

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 4.   C.A.,  22. (1972)  141710H Use of soap in modern detergent
      formulations.   Noble,  W. R.;  Bistline,  R.  G.,  J.;
   '   Linfield,  W. M.  (East  Reg.  Res. Lab.,  Agric.  Res.  Serv.,
      Philadelphia,  Pa.)  Soap, Cosmet.,  Chem.  Spec.  1972,  48(7),
      38-42, 62.

 5.   U.S.  Patent 3,660,470  Lime  soap dispersants and compositions
      containing them.   David Graham Spencer Hirst to The  Procter
      and Gamble Company,  May 2,  1972.
           Alkylbenzyl  di-lower alkylammonio alkane-1 sulfonates.
           These are zwitterionic surfactants.

 6.   C.A.,  7 (1972)  115207J Soap compositions  containing alkyl
      amino diacetates  as lime soap dispersants.  Shen,  Chung Yu
      (Monsanto  Co.) U.S.  3,630,927, 28 December 1971, 2 pp.

 7.   C.A.,  2 (1972)  15990r Soap compositions containing  vicinal
      hydroxyalkyl maleates.  Kidwell,  Roger L.; Payne,  John H.
      (Monsanto  Co.) U.S.  3,607,762, 21 September 1971,  3  pp.
           167. of the title  compound (alkyl=Cig) plus 84%  soap
           used  as lime resistant washing composition.

 8.   C.A.,  77 (1972)  141718s Alkyl vic-hydroxyalkoxy ether
      maleate compounds.   Kidwell,  Roger L.  (Monsanto Co.)
      U.S.  3,686,282,  22 August 1972, 3 pp.
           16% of the title  compound (alkyl=Cx6) plus 84%  soap
           used  as lime resistant bar.

 9.   C.A.,  22. (1972)  21998m Detergent compositions comprising
      mixtures of surface-active  compounds.   Bakker, Pieter M.
     ' (Shell Internationale  Research Maatschappij N.V.)
      Brit.  1,269,919,  6 April 1972, 5 pp.
           Sodium salts of Ci2-20 monocarboxylic acids made by
           Reppe carbonylation of olefins.  These have high
           tolerance.

10.   C.A.,  72 (1972)  154320f Detergent compositions.
      Davies, James  Francis; Gauterin, Charles Rowland;
      Gilbert, Phillip Alan  (Unilever N. V.) Ger. Offen. 2,204,865,
      17 August  1972,  25 pp.
           20-60% sodium laurate  plus 10-50% alkylbenzene sulfonate,
                           221

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E.   Representative Carbonate-Silicate Formulations:
     1.   C.A., 21 (1972) 116391x Phosphate-free detergents.
          Benjamin, Lawrence; Saylor, Jay Harold (Procter and Gamble
          Company) Ger. Offen. 2,161,699, 29 June 1972, 33 pp.
               Fatty alkyl sulfates, alkoxy-and acyloxy- alkane sul-
               fonates used with 25% silicate and 25% carbonate.

     2.   U.S. Patent 3,708,428 Detergent compositions containing
          silica colloids.  Louis McDonald, January 2, 1973.

     3.   C.A., 2 (1973) 45428x Phosphate-free detergent compositions.
          Morton, Edgar J.; Donnan, Harold; Weisenfeld, Arnold (Witco
          Chemical Corp.) Ger. Offen. 2,218,763, 16 November 1972,
          16 pp.
               Carbonate-silicate builder.

     4.   C.A., 2. (1972) 129210s Phosphate-free detergents.
          Cooper, Robert S.; Koschak, Joseph; Wood, Donald C.
          (De Soto Inc.) Ger. Offen. 2,124,729, 20 January 1972, 19 pp.
               High percentage carbonate-silicate builder.
F.   Ion Exchange Resins as Builders:

     1.   C.A., 21 (1972) 77077c Divinylbenzene copolymer-containing
          detergents.  Frankenfeld, Klaus; Goetzmann, Karl;
          Pietruck, Christel (Chemische Fabrik Budenheim Rudolph A.
          Oetker K.-G.) Ger. Offen. 2,055,423, 18 May 1972, 10 pp.
               Sulfonated styrene-divinylbenzene, and acrylic acid-
               divinyIbenzene.

     2.   U.S. Patent 3,721,627 Builder for phosphate-free detergent
          compositions.  James  William Adams, Henry Wilbert Hoftiezer
          to American Can Company,  March 20, 1973.
               Insoluble cellulose-polyacrylic graft used in pulp
               or powder form.
                               222

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                             APPENDIX E

                CHRONIC AQUATIC  TOXICITY TESTS
                  A Summary of Chronic Test Procedures
                    and Results for Test Sample 64-1
     In order to establish a possible chronic toxicity profile for test
sample 64-1 a number of biological tests were performed.  Test sample
64-1 was tested against nine aquatic organisms and in addition histological
studies of effects upon fish gill tissue and upon fish egg viability were
also performed.  The test  exposure periods varied because of differences
in the nature of the life  cycle of the various test organisms.  In addition,
although most of the test  organisms were exposed to two temperatures and
three test dilution waters, not all the test organisms could be subjected
to the desired temperatures and waters.

     Three test dilution waters, a soft, a hard, and a high alkaline
water,were synthesized using typical waters with these characteristics
found in the United States.    Two temperatures,18C and 30C,were the
test temperatures.

     Three test concentrations were incorporated, derived from the acute
tests of 64-1.  These concentrations were, the highest concentration
allowing 1005? survival of  the  most sensitive organism over the 96-hour
test period, a theoretical biologically safe concentration calculated by
dividing the median tolerance  concentration by one hundred, and a con-
centration mid-way between the two.  The most sensitive test  organism was
the blucgili sunfish and  the highest concentration allowing complete
survival was 18 ppm.  The other  two test concentrations were  0.18 ppm
and 8.7 ppm.

     In all tests continuous flow techniques were used and  the methods
and procedures for the continuous  flow procedures were  the  same as
described in the acute test  reports.   The  crustacean  and  insect were
not tested acutely and these test  procedures are described  in this  report.

     The following chart lists the test organisms,  length of  exposure  to
64-1, test dilution waters and test  temperatures incorporated.

1,
Exposure
Test Organism Time
Bluegill sunfish 60 days
Lepomis macrochirus Raf.

Dilution
Water
soft
hard
alkaline
Temp.
18C
30*C
2.  Bullhead catfish                   60 days            soft       18C
    Amoiurus nobulosus                                    hard       30*C
                                                          alkaline

                                223

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3.
4.
5.
6.
7.
8.
9.
Ter.t Organism
Brook trout
Salvclinus, fontinclis

Pond snail
Physa heterostropha Say
Gilled snail
Amnicola limosa Say

Diatom
Navicula seminulum var.

Diatom
Nitzschia pa lea

Crustacean
Daphnia pul sx
Insect mayfly
Isonychia bicolor

Exposure
Time
60 days
60 days
60 days
14 days
hustedtii

14 days
40 days
25 days
Live fish egg studies were performed on the
Dilution
Water
soft
hard
alkaline
soft
hard
alkaline
soft
hard
alkaline
soft
hard : . .
alkaline
soft
hard
alkaline
soft
hard
alkaline
soft
hard
alkaline
flagfish Jordanella
Temp.
18C
18C .
30*C
18C
30C
18C
18'C
18C
30C
15
floridae
 and histological gill investigations  were  performed on  the bluegill sunfish '
 and catfish gills exposed for  sixty days to  the  test material 64-1.

                                       Results

 I.  Bluegill sunfish, Lepomis  macrochirus  Raf,.
     A.  No death at any test concentration over  the sixty day test period.
     B.  No noticeable gross changes in feeding habits,  general health or
         general behavior during  the sixty  day test period.

II.  Bullhead catfish, Ameiurus nebulosus
     A.  No death at any test concentration over  the sixty day test period.
     B.  No noticeable gross changes in feeding habits,  general health or
         general behavior during  the sixty  day test period.
                                  224

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  II.  Brook trout, Salvelinus font!nails
       A.   No death at  any  test concentration over the sixty day test period.
       B.   No noticeable  gross changes in feeding habits, general health or
           general behavior during the sixty day test period.

 IV.   Pond snail, Physa  heterostropha Say
       A.   No death at  any  test concentration over the sixty day test period.
       B.   Reproduction proceeded normally and one generation was produced
           during the sixty day test period.

 V.     Gilled snail, Amnicola limosa Say
       A.   No death at  any  test concentration over the sixty day test period.
       B.   No eggs were produced in test concentrations or controls during
           the sixty day  test period.  At the same time eggs were produced
           in the Amnicola  culture tanks.

 VI.   The diatom Navicula  seminulum var. hustedtii
Test
Concentration
0.18 ppm
,8.7 ppm
18.0 ppm
Control
Alkaline
Test Water
166?o growth
115% growth
120% growth
100J5 growth
Soft
tTest Water
108% growth
137J6 growth
715? growth
100% growth
Hard
Test Water
10455 growth
1325? growth
11695 growth
100J6 growth
 VII,   The diatom Nitzschia  palea
 0.18 ppm
 8.7 ppm
18.0 ppm
 Control
134J5 growth
106% growth
 84% growth
10052 growth
                                         144J6 growth
                                         150JS growth
                                         124% .growth
                                         100% growth
168J6 growth
132% growth
165% growth
100$ growth
 VIII.  Crustacean Daphnla  pulex
        Ten pregnant females  were placed  in  the continuous  flow test chambers
 containing the experimental  dilutions  and control.   All tests were done in
 duplicate.  The number of  eggs in each brood  pouch  were counted and those
 not maturing were considered aborts.   Young,  born and  living for 24 hours
 were counted and all but ten were removed from the  test chambers* these
 ten were first generation  test organisms.   This process was  repeated for
 three generations over a forty day test  period.
Test Cone.    Alkaline Test Water

Control       100% survival of all
              test organisms with no
              aborts through three
              generations.  A total
              of 228 eggs were
              produced*
                                         Soft Test Water    Hard Test Water
                                         10QSE survival of
                                         all test organisms
                                         with no aborts
                                         through three
                                         generations.  A
                                         total of 232 eggs
                                         were produced.
                                           100JS survival of all
                                           test organisms with
                                           no aborts through
                                           three generations.
                                           A total of 244 eggs
                                           were produced.
                                     225

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Test Cone.
Alkaline Tost Wnter
Soft Test Water
Hard Test Water
0.18 ppm      Same as control.
              A total of 243 eggs
              were produced.
                         Same as control.
                         A total of 251 eggs
                         were produced.
                        Same as control.
                        A total of 229 eggs
                        were produced.
8.7 ppm       100?5 survival of
              original 20 test
              organisms, 84 eggs were
              produced, 3/5 aborted
              and 5% of the young
              died.  The 20 test
              organisms in the first
              generation produced 9
              eggs and 100JS aborted.
                         100?o survival of
                         original 20 test
                         organisms, 74 eggs
                         v.-cre produced, 3$
                         aborted and 5/o of the
                         young died.  The 20
                         test organisms in the
                         first generation pro-
                         duced 10 eggs, and
                         100J5 aborted.
                        100JS survival of
                        original 20 test
                        organisms, 87 eggs
                        were produced, 2/6
                        aborted and 49? of
                        young died.  The 20
                        test organisms in
                        the first generation
                        produced no eggs.
18 ppm
0# survival of original
20 test organisms in
24 hours.
0# survival of
original 20 test
organisms in 4 days.
0% survival of
original 20 test
organisms in 5 days.
Control       100?5 survival of all
              test organisms with no
              aborts through three
              generations.  A total
              of 243 eggs were pro-
              duced.
                        30C

                         100# survival of all
                         test organisms with no
                         aborts through three
                         generations.  A total
                         of 241 eggs were pro-
                         duced.
                        10006 survival of all
                        test organisms with no
                        aborts through three
                        generations.  A total
                        of 265 eggs were pro-
                        duced.
0.18 ppm      Same as control.  A
              total of 267 eggs
              were produced.
                         Same as control.  A
                         total of 278 eggs were
                         produced.
                        Same as control.  A
                        total of 249 eggs
                        were produced.
8.7 ppm       100% survival of
              original 20 test
              organisms.  96 eggs
              were produced, 2#
              aborted and 4.7J5 of
              the young died.  The
              20 test organisms in
              the first generation
              produced 12 eggs and
                   aborted.
                         100JS survival of orig-
                         inal 20 test organisms.
                         86 eggs were produced
                         1% aborted and A% of
                         young died.   The 20
                         test organisms in the
                         first generation pro-
                         duced 6 eggs, 100JS
                         aborted.
                        1005? survival of
                        original 20 test
                        organisms.  98 eggs
                        were produced, 1%
                        aborted and 5% of
                        young died.  The 20
                        test organisms in the
                        first generation pro-
                        duced no eggs.
IGppm
05S survival of orig-
inal 20 test organisms
in 24 hours.
053 survival of orig-
inal 20 test organisms
in 5 days.
OJ6 survival of orig-
inal 20 test organisms
in 5 days.
                                 226

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IX.  Insect I^sonychia bicolor
     Ten mature nymphs measuring  about  1  to  1.5 cm in  length not  including
tail were placed in the continuous  flow test chambers  containing  the  experi-
mental dilutions and control.   All  tests  wore done in  duplicate.   The tests
wore allowed to proceed until  all nymphs  reached  the sub  imago and adult
stage.  Tests were conducted at 15C.   There were no deaths at any test con-
centration or control in any dilution water  and all nymphs emerged successfully
after 25 days of exposure.

X.  Gill histology,sunfish  and catfish
    Five fish were sacrificed  from  each concentration  at  each temperature in
each dilution water at the  end of thirty  days  exposure and sixty  days exposure.
Gill slides were prepared according to  techniques as stated in Cairns and
Scheier, 1963.  There were  no  apparent  histological effects seen  in either
sunfish or catfish gills at concentrations of 0.18 or  8.7 ppm.  At 18 ppm
slight "clubbing" and adherence of  gill lamellae  were  observed after 60 days
of exposure in both sunfish and catfish.  This  effect  could also  be seen  in
the controls but its incidence appeared to be greater  at  18 ppm.   No  epithelial
stripping or capillary rupture was  observed.

XI.  Survival of Jordanella embryos and fry
     Twenty-five, twenty-four  hour  old  Jordanella eggs were placed in test
chambers containing the test dilutions  in soft, hard and  alkaline water.   Each
test was done in triplicate and the test  temperature was  30C.  Hatching
occurred between the fourth and fifth day and  the fry  were observed for  twelve
days.  The  following chart lists average %  survival after seventeen days.

Test Water      Control             0.18  ppm      8.7  ppm        18 ppm

soft            74.64J6               7256           7856           6256
hard            78.8456               925?           7656           92J6
alkaline        89.3256              -9256            9256           8456

     It should be noted that  this fish  does  not naturally occur in soft water,

Summary:

     The only profound effects of the test material at the  experimental con-
centrations appear to be its  stimulatory effect upon diatom growth at all
concentrations and its extremely toxic  effect upon Daphnia  at the 8.7 ppm
and 18 ppm levels.  We are proceeding with high temperature diatom tests
after having received two species of diatoms able to withstand the 30QC  test
temperature.

Literature Cited

Cairns, Jr., J,  , and Scheier, A.  "The Acute and Chronic Effects  of Standard
Sodium Alkyl Benzene  Sulfonate Upon the Pumpkinseed Sunfish, Lepomis gibbosus
(Linn.) and the  Blueglll Sunfish L. macrochirus Raf."  Proc. 17th Industrial
Waste Conf. Eng. Ext. Ser. Series~No.  112 Purdue University, 1963.

                               227

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            A Summary of Chronic Test Procedures and Results
                        for Test Sample 86-700 (AATCCWOB)
      In order to establish a possible chronic toxicity profile for test
sample 86-700, a number of biological tests were performed. Test sample
86-700 was tested against nine aquatic organisms and in addition histo-
loglcal studies of effects upon fish gill tissue and upon fish egg via-
bility were also performed*  The test exposure periods varied because of
differences in the nature of the life cycle of the various test organisms*
In addition, although most of the test organisms were exposed to two
temperatures and throe test dilution waters, not all the test organisms
could be subjected to the desired temperatures and waters.

     Three test dilution watersa soft, a hard, and a high alkaline
waterwere synthesized using typical waters with these characteristics
found in the United States.  Two temperatures18C and 30Cwere the
test temperatures, except for the insect tests which were  done at 15C.

     Three test concentrations were incorporated, derived  from the acute
tests of 86^-700.  These concentrations were (1) the highest concentration
allowing 100K survival of the most sensitive organism over the 96-hour
test period, (2) a theoretical biologically safe concentration calculated
by dividing the median tolerance concentration by one hundred, and (3) a
concentration mid-way between the two.  The most sensitive test organism
was the bluegill sunfish and the highest concentration allowing complete
survival was 13.5 ppm.  The other two test concentrations  were 6.5 ppm
and 0.153 ppm.

     In all tests continuous flow techniques were used and the methods and
procedures for the continuous flow procedures were the same as described
in the acute test reports.  The crustacean and insect were not tested
acutely, and these test procedures, are described in this report.

     The following chart lists the test organisms,  length  of exposure to
86-700, test dilution waters, and test temperatures.
    Test Organism
Exposure
  Time
Dilution
 Water
Temp,
1.  Bluegill sunfish
    Lepomis macrochirus  Raf.
 60 days
 soft
 hard
 alkaline
18c
30C
                                 228

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    Test Organism
Exposure
.- Tiina
Dilution
 Water
Temp.
2.  Bullhead catfish
    Ameiurus nebulosus
 60 days
 soft
 hard
 alkaline
180C
30C
3.  Brook trout
    Salvelinus fontinelis Mitchell
 60 days     soft
             hard
            180C
4.  Pond snail
    Physa heterostropha Say
 60 days     soft        18C
             hard        30C
             alkaline  
5.  Gilled snail
    Amnicgla limosa Say
 60 days     soft        18C
             hard        30C
             alkaline
6.  Diatom                              14 days
    Navicula seminulum var. hustedtii Patr.
             soft
             hard
             alkaline
            18C
7.  Diatom,
    Gompho'nema parvulum
  14 days
 soft
 hard
 alkaline
 18C  -
8.  Crustacean
    Daphnia pulex
  40 days
 soft        18C
 hard        30C
 alkaline
9  Insect (mayfly)
    Isonychia bicolor
  25 days
 soft
 hard
 alkaline
 15C
     Histological gill investigations were performed on the bluegill sun-
fish and catfish gills exposed for sixty days to the.test material 86-700.
                                  229

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                                RESULTS
 I.    Bluegill  sunfish,  Leponds  macrochirus  Raf.

      A.  No  death at any test concentration over the  sixty-day  test  period.
      B.  No  noticeable  gross changes  in  feeding  habits,  general health, or
         general behavior during  the  sixty-day test period.

 II.   Bullhead  catfish,  Ameiurus nebulosus

      A.  No  death at any test concentration over the  sixty-day  test  period*
      B.  No  noticeable  gross changes  in  feeding  habits,  general health, or
         general behavior during  the  sixty-day test period.

 III.  Brook trout. Salvelinus fontinalis  Mitchell

      A.  No  death at any test concentration over the  sixty-day  test  period*
      B.  No  noticeable  gross changes  in  feeding  habits,  general health, or
         general behavior during  the  sixty-day test period.

 IV.   Pond snail, Physa  heterostropha  Say

      A.  No  death at any test concentration over the  sixty-day  test  period*
      B.  Reproduction proceeded normally, and  one generation was produced
         during the sixty-day test period.

V.    Gilled  snail, Amnicola limosa Say

      A.  No  death at any test concentration over the  sixty-day  test  period*
      B.  Eggs were produced in  all test  concentrations,  but no  hatching was
         observed.

VI.   The diatom Navicula seminulum var.  hustedtii Patr.

      Test                 Alkaline             Soft              Hard
      Concentration       Test Water          Test Water        Test Water

      0.153  ppm         147.456 growth       105.656 growth    153.656  growth
      6.5 ppra           333.356 growth       177.8^ growth    139.356  growth
      13.5 ppm           284.456 growth       130.996 growth    139.356  growth
     Control            10056 growth         10056  growth       10056 growth

VII. The diatom, Gomphonema  parvulum

      0.153             170.458 growth       58.556 growth    140.556  growth
      6.5 ppm           199.156 growth       72.156 growth    154.556 growth
     13.5 ppm           162.156 growth       115.356 growth     140.456  growth
     Control            10056 growth         10056 growth       10056 growth

                                230

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VIII.  Crustacean, Daphnia pulex
     Ten pregnant females were placed in the continuous flow test chambers
containing the experimental dilutions and control.  All tests were done in
duplicate*  The number of eggs in each brood pouch'were counted and those
not maturing were considered aborts.  Young, born and living for 24 hours,
were counted and all but ten were removed from the test chambers.  These
ten were first generation test organisms.  This process was repeated for
three generations over a forty-day test period.
Control
 Alkaline Test Water

100% survival of all
test organisms with
no aborts through 3
generations.  Total
of 241 eggs were
produced*
  18C

  Soft Test Water

10056 survival of all
test organisms with
no aborts through 3
generations.  Total
of 256 eggs were
produced.
  Hard Test Water

10056 survival of all
test organisms with
no aborts through 3
generations.  Tota1
of 233 eggs were
produced.
0*153     Same as control. A
ppm       total of 236 eggs
          were produced.
                      Same as control. A
                      total of 240 eggs
                      were produced.
                      Same as control. A
                      total of 247 eggs
                      were produced.
6*5       8056 survival, 1st
ppm       generation test or-
          ganisms)  94 eggs
          produced, 9.556 abort-
          ed, 14% young died.
          6556 survival, 2nd
          generation; 30 eggs
          produced, 26.356
          aborted, 31.556 young
          died.  90% survival,
          3rd generation; 27
          eggs produced, 35.756
          aborted, 50$ young
          died.
                      9096 survival, 1st
                      generation test or-
                      ganisms}  86 eggs
                      produced, 756 abort-
                      ed, 2056 young died*
                      8056 survival, 2nd
                      generation; 29 eggs
                      produced, 31.256
                      aborted, 37.556 young
                      died.  8556 survival,
                      3rd generation; 22
                      eggs produced} 50$
                      aborted, 3056 young
                      died.
                      8556 survival, 1st
                      generation test or-
                      gan isms >  63 eggs
                      produced, 4*756 abort-
                      ed, 17$ young died*
                      9056 survival, 2nd
                      generation; 31 eggs
                      produced, 26.356
                      aborted, 33.356 young
                      died.  8555 survival,
                      3rd generation; 17
                      eggc produced; 30%
                      aborted, 5056 young
                      died.
13.5      OX survival, 1st
ppm       generation test or-
          ganisms in 10 days.
          24 eggs produced,
          956 aborted, no
          young born.
                      0$ survival* 1st
                      generation test or-
                      ganisms in  6 days.
                      18 eggs produced,
                      6.356 aborted, no
                      young born.
                      Of survival,  1st
                      generation  test or-
                      ganisms  in  11 days.
                      23 eggs  produced,
                      7.45?  aborted,  no
                      young  born.
                                 231

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                                   30C

            Alkaline  Test  Water    Soft Test Water
                        Hard  Test Water
 Control    1005? survival  of all   10056 survival  of  all   10053 survival  of  all
           test organisms  with
           no aborts  through 3
           generations.  Total
           of 231  eggs were
           produced.
test  organisms with
no aborts through 3
generations.  Total
of 210 eggs were
produced*
test  organisms with
no aborts through 3
generations.  Total
of 254 eggs were
produced.
0.153     Same as control. A
ppm       total  of 225  eggs
          were produced.
Same as control.  A
total of 163 eggs
were produced.
Same as control.  A
total of 239 eggs
were produced.
6.5       8556 survival,  1st
ppm       generation test or-
          ganisms ; 96 eggs
          produced, 3.1% abort-
          ed, 4.85? young died.
          855? survival,  2nd
          generation; 34 eggs
          produced, Q% abort-
          ed, 31.85? young died.
          1005? survival, 3rd
          generation; 10 eggs
          produced, 20??  abort-
          ed, 42.95? young died.
8055 survival, 1st
generation test or-
ganisms; 38 eggs
produced, 10.55? abort-
ed, 13.15? young died,
5056 survival, 2nd
generation.  No eggs
produced in remain-
ing test organisms
of 2nd generation.
05% survival, 1st
generation test or-
ganisms; 101 eggs
produced, 3.95? abort-
ed, 11.356 young died.
855? survival, 2nd
generation; 21 eggs
produced, 0% abort-
ed, 42.156 young died.
9556  survival, 3rd
generation; 19 eggs
produced, 15.556 abort-
ed, 056 young died.
13.5      056 survival, 1st
ppm       generation test or-
          ganisms after 9 days,
          42 eggs produced,
          16.656 aborted, 10056
          young died.
0% survival, 1st
generation test or-
ganisms after 7 days,
24 eggs produced,
25% aborted, no
young born.
05? survival, 1st
generation test or-
ganisms after 13 days,
35 eggs produced,
205? aborted, no
young born.
IX.  Insect, Isonychia bicolor

     Ten mature nymphs measuring about 1 to 1.5 cm in length, not including
tail, were placed in the continuous flow test chambers containing the experi-
mental dilutions and control.  All tests were done in duplicate.  The tests
were allowed to proceed until all nymphs reached the sub-imago and adult
stage.  Tests were conducted at 15C.  There were no deaths at any test
concentration or control in any dilution water and all nymphs emerged
successfully after 25 days of exposure.
                                232

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X.  Gill Histologysunfi?h and catfish

     Five fish were sacrificed from each concentration at each temperature
in each dilution water at the end of thirty days'  exposure and sixty days'
exposure.  Gill slides were prepared according to  techniques outlined in
Cairns and Scheier (1963).

     Histological effects were seen at all concentrations in all dilution
waters at the two test temperatures.  At 30 days small amounts of epithalial
stripping could be detected in both bluegills and  catfish in all dilution
waters and temperatures at all three concentrations.   The intensity of the
stripping varied directly as the test concentration increased.  At 0.153 ppm
approximately one-third of the examined gills showed  some epithelial strip-*
ping, while 7558 of the 6*5 ppm gills showed effects*   Almost all the 13*5 ppm
gills showed some epithelial stripping after 30 days' exposure.  After 00
days1 exposure about 50JS of the 0.153 ppm gills showed effects in all dilu-
tion water and temperatures.  Almost all 6.5 ppm and  13*5 ppm gills were
affected after 60 days' exposure.

XI.  Survival of Jordanella embryos and fry

     Twenty-five 24-hour old Jordanella eggs were  placed in te,st chambers
containing the test dilutions in soft, hard, and alkaline water.  Each test
was done in triplicate and the test temperature was 30C.  Hatching occurred
between the fourth and fifth day, and the fry were observed for twelve days*
The following chart lists average percent survival after seventeen days.

  Test Water         Control        0.153 ppm      6,5 ppm      13.5 ppm

   Soft               94.558           96.055         80.0*         69.358
   Hard               88.058           82.658         86.6?         78.658
   Alkaline           92.0%           89.358         76.0$         81.358

     It should be noted that this fish does not naturally occur in soft
water.
                                233

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                                SUMMARY
     The marked effects of  this  test material appeared to be its stimulatory
effect upon diatom growth at almost all  concentrations, its toxic effect
upon Daphnia at the 6.5 ppra and  13.5 ppm level,  and histological changes in
gill tissue at all concentrations.  All  effects  were, for the most part,
independent of dilution water or temperature.
                           LITERATURE  CITED
Cairns, J. Jr. and A. Scheier.   1963.  The  acute  and  chronic  effects  of
     standard sodium alkyl benzene sulfonate upon the purapkinseed sunfish,
     Lepomis gibbosus (Linn.) and the bluegill  sunfish L.  macrochirus Raf.
     Proceedings 17th Industrial Waste Conf, Eng. Ext. Series No. 112,
     Purdue University.
                                  234           *US. GOVERNMENT PRINTING OFFICE: 1974 546-316/Z79 1-3

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SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM  EPA-600/2-

4. Title
                                                        Accession ffo.
7. .4 uthor(s)
          The Development of Phosphate Free Heavy
                Duty Detergents

             Schwartz, A.M. and Davis, S.E.
9. Or_T,m nation
             Gillette Research Institute
             1413 Research Boulevard
             Rockville, Maryland   20350
                                                      in. Project No.

                                                          16080 FWF-
                                                      >. Contract/Grant fr;.

                                                            14-12-875
                                                                  and
75.  Supplementary Notes
                Project Officer:  Dr. A.  Forziati, OR & D
                U.S. EPA, Washington, D.C.
is.  Abstract rpft& purpose of tliis project was  to demonstrate state-of-the-art
   possibilities for producing phosphate-free household laundry deter-
   gents of satisfactory environmental and performance characteristics.
   The work involved formulation of several hundred experimental  deter-
   gent compositions using different surfactant-builder combinations.
   These were tested for laundering performance, acceptability of physi-
   cal form, biodegradability, aquatic toxicity, potential hazard in use,
   and growth stimulation of algae.  Feasibility of economical production
   on an. industrial scale was also considered.  Some partially satisfac-
   tory formulations were found, and their shortcomings assessed  with
   regard to performance and/or economic  feasibility.  These  formulations
   coincide remarkably with formulations  developed independently  by
   industry.  Further work with promising new builders and surfactant-
   builder combinations is recommended, but only along environmental and
   health hazard lines.  This report was  submitted in fulfillment of
   Project No. 16080 FWE and Contract  No. 14-12-875 by Gillette Research
   Institute under the sponsorship of  the Environmental Protection Agency
   Work was completed as of November 30,  1973.
17a. Descriptors
17b. Identifiers
             Economic Analysis
             Detergents
             Surfactants
             Toxicity
             Phosphate-Free
                                         Water Quality
                                         Soaps
                                         Biodeterioration
                                         Water Pollution
17c. COWRRField & Group   05C/05B
18.  Availability

   unlimited


Abstractor
                                             Send To:


                                             WATER RESOURCES SCIENTIFIC INFORMATION CENTER
                                             U.S. DEPARTMENT OF THE INTERIOR
                                             WASHINGTON. O. C. 2O24O
                                In&titutior.

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