25, 1962.

Four meetings have been held during the ensuing time. Recently, it was concluded that it would be beneficial to have a representative from the U.S. Public Health Service as an ex officio member of this subcommittee. I have written to Dr. Gordon E. McCallum, Assistant Surgeon General of the U.S. Public Health Service, in this regard and have solicited his nomination for such an individual. I am pleased to be able to report that Dr. McCallum has appointed Dr. Leon Wienberger, Chief, Basic and Applied Sciences Branch, Division of Water Supply and Pollution Control, U.S. Public Health Service, and an ex officio member of the industry's biodegradation test method subcommittee.

After a review of various methods in use in member laboratories, the first method which the group agreed to consider cooperatively was a river-die-away test. This is a rather simple test which employs natural river water to which the product under study is added. The biodegradation or decomposition of the surfactant is followed by chemical analysis over a period of time until no further degradation is evident. In this first study, a composite sample of propylene tetramer alkyl benzene sulfonate, supplied by the Soap and Detergent Association and typical of the common article of commerce, and a secondary straight-chain alkyl benzene sulfonate, prepared from dodecene-1, were examined in 35 rivers. From this work, it was clear that not all rivers could be used with this method. The most probable reason seemed to be that in certain instances the bacterial population of the water was too low. A second difficulty in at least one instance was that a river apparently contained substances which interfered sufficiently with the analytical method to cause erroneous and erratic results. A second series of cooperative studies, wherein a minimum bacterial count was a prerequisite, provided much more consistent data. Other conclusions were (1) that with the dodecene-l derived material the initial rate or lag time in apparent degradation was a function of initial concentration, and (2) that the results with either material were not affected by light.

While not specifically a part of the cooperative studies, a number of other contributions to an understanding of the river-die-away test were made by several of the member laboratories and reported to the subcommittee. This work indicates, for example, that the results in many instances were definitely related to prior exposure of the bacteria to the test material in question, such that if adaptation is permitted, the results are quite different. Precaution should be exercised with this method, therefore, in attaching undue significance to differences between materials, especially in the initial, apparent rates of degradation. The committee's evaluation of the river-die-away procedure, in summary, is that it is not suitable as a standard industry method, but can be very useful where allowance is made for the factors mentioned above.

Most recently, the subcommittee has elected to undertake a cooperative study of an activated sluge test method. In this test, the surfactant is exposed to microbial flora developed from sewage by the forced addition of relatively large amounts of air. It is continuous in that the test surfactant and nutrient medium are supplied in a constant manner and the reacted mixture removed similarly. In general, such a test simulates the secondary process followed in many modern sewage treatment plants, and is the type of test which many people feel would be most readily acceptable to those professions concerned with waste disposal. Initial work with this method follows a procedure adapted from one used successfully by a member laboratory over a period of several years. It differs from the recent official German method in that (1) the synthetic feed medium is inoculated with bacteria from sewage, (2) uses better mixing and (3) uses smaller sized apparatus. In addition, it is anticipated that the length of the time required for each test will be considerably less than that with the German method. In the German method, the amount of time involved is perhaps its most objectionable feature. This cooperative study is now in progress and every effort is being made to have a suitable test available in the very near future.

In conclusion, and as a representative of Continental Oil Co., I am further privileged to submit the following excerpts from a letter, written by Mr. E. R. Baker, general manager, research and petrochemical departments, to the Honorable Anthony Celebrezze, Secretary of Health, Education, and Welfare, on June 3. This letter presents Continental Oil Co.'s plans and position with respect to the commercial manufacture of intermediates for biodegradable detergents:

"On May 15, 1963, Continental's board of directors approved a capital expenditure of more than $7 million for the construction of new and conversion of present facilities to produce 'Nalkylene' detergent alkylate. This new material is a straight-chain product which, when converted into the finished detergent, is biodegradable. It is expected that these facilities will be completed early in the summer of 1964 and that substantial quantities will be in the hands of the detergent manufacturers by September of 1964. These manufacturers then will have for the first time a commercial product for the formulation and process development necessary to provide satisfactory end-use materials.

"In addition to the 'Nalkylene' alkylate plant, Continental Oil has been producing 'Alfol' detergent alcohols for over a year at a $10 million plant. 'Alfol' alcohols derived from petroleum sources, provide a raw material which when sulfated, ethoxylated, or ethoxylated and sulfated produces blending components for liquid detergents which are also biodegradable.

"I would like to take this occasion to respond to recently voiced accusations that the Soap & Detergent Association and several large detergent manufacturers have been delaying the introduction of new products designed to overcome the 'detergent' problem. On the contrary, as a supplier we have been continuuously encouraged to rush the development of our 'Nakylene' and 'Alfol' materials. Continental Oil itself has expended upward of $6 million in research on the two types of products described and will have invested nearly $20 million in facilities designed specifically to produce new detergent raw materials which can alleviate the industry's share of the water-pollution problem. Due to the highly com petitive nature of this industry both in the finished household product area as well as in the raw materials supplier area much of the very substantial progress made has not become known generally.

"We appreciate the opportunity to assure you that both segments of the industry are indeed making major efforts to solve the water pollution problem in a voluntary fashion."

STATEMENT OF RICHARD B. WEARN, DIRECTOR OF RESEARCH. COLGATE-PALMOLIVE Co., AND VICE CHAIRMAN, TECHNICAL & MATERIALS DIVISION, RESEARCH COMMITTEE, THE SOAP & DETERGENT ASSOCIATION

Honorable Chairman and members of the Special Subcommittee on Air and Water Pollution, I am Dr. Richard B. Wearn. I am a director of research for the Colgate-Palmolive Co., where I am responsible for all research and development work on soap and detergent products. I have also participated regularly as a member of the Technical and Materials Research Committee of the Soap & Detergent Association, and am currently serving as vice chairman.

I hold the degrees of bachelor of science in chemistry from Clemson College (1937), and Ph. D. in organic chemistry from the University of Illinois (1941), Serving as captain in the Chemical Corps during World War II, I was engaged in research on the development of organic chemical warfare agents and on methods for detection and removal from air and ground surfaces. Since that time, I have been engaged in industrial research and development on organie chemicals and synthetic detergents, and for the past 15 years have directed the research program of the Colgate-Palmolive Co. on its soap and detergent products. I would like to tell you about the research which our industry has been conducting since synthetic detergents were first detected as residues in sewage and waste waters some years ago.

Beginning about 12 years ago, reports of unusual frothing in sewage treatment plants and occurrences of foam on the surface of streams came to the attention of soap and detergent manufacturers and to the Soap & Detergent Association. In some cases, chemical analysis indicated the presence of residual synthetic detergents in the water.

The attention of our industry, of sanitation and water treatment authorities. and of Government agencies concerned with water quality and pollution control was promptly directed to these incidents. Surveys were conducted, monitoring of rivers and water supplies was initiated, and research was initiated to develop reliable analytical and assay methods to be employed in determining the extent to which detergents did exist in water supplies and the behavior of these materials in various types of sewage disposal systems. Our industry played a leading role in this important early phase of the research and it was largely through our efforts that analytical test methods and laboratory procedures were standardized, published, and made generally available to laboratory researchers.

It was not long before the material known as propylene tetramer alkyl benzene sulfonate (commonly called ABS) was identified as the detergent present in some sewage plant effluent and in some rivers and water supplies. This material is the most widely used detergent and is present in approximately 75 percent of the packaged consumer products sold today. We learned that it behaves differently from most organic waste in that it is resistant to decomposition by biological oxidation in sewage treatment processes and by the naturally occurring microorganisms in rivers and water supplies.

The sewage and water treatment authorities have directed their attention to improving the processes of decomposition and removal of ABS, and have indeed made considerable progress. Our industry and the technical committees of the Soap & Detergent Association have maintained close liaison with other technical groups working in this field and have participated in research programs of this type in many locations throughout the country. Research projects are also sponsored by the Soap & Detergent Association at a number of leading universities and industrial laboratories in this field including:

Massachusetts Institute of Technology: Sanitary Engineering Department. University of Wisconsin: Laboratory of Hydraulics and Sanitary Engineering.

University of Wisconsin: Department of Botany.

University of Illinois: Department of Civil Engineering.

University of California: Sanitary Engineering Research Laboratory.

Johns Hopkins University: Department of Sanitary Engineering and Water”
Resources.

Rolf Eliassen Associates.

Arthur D. Little, Inc.

There are indications that practical measures are being developed which will largely eliminate ABS from sewage and waste water.

Nevertheless, our industry has no intention of waiting for such developments to solve the problem. Foaming in water supplies and in streams is acknowledged to be objectionable. We are determined to eliminate ABS detergent from our products as soon as it is feasible to do so, and thus to eliminate any foaming to which ABS is a contributing factor. To this end, the manufacturers of household detergents and the suppliers of the principal raw materials individually are extensively engaged in research to find readily decomposable detergents which may be substituted for ABS.

Such work is very complex. The search in each research laboratory begins with the screening of all known detergents and of many newly synthesized materials from the laboratory in a cooperative effort of chemists and microbiologists, who are able to classify types of materials which are readily decomposable and to relate molecular structure to susceptibility to microbiological attack. From this information, researchers are in a position to deduce the mechanism by which the organisms decompose the detergent molecules, and to design optimum molecular structures from theoretical considerations. Though somewhat time consuming, this approach has been highly successful, and a number of materials have been found which are highly decomposable in a laboratory test environment.

These selected materials are put through extensive formulation studies in product development laboratories of the various detergent manufacturers, to find those best suited for the primary functional usage for the products such as dishwashing, floor and wall cleaning, and laundering in various types of washing machines. Concurrently, all aspects of safety and exposure to these materials during customary use or accidental misuse by consumers is carefully checked out, and any unsatisfactory materials eliminated from further consideration. Finally, the most suitable material is selected by each manufacturer for largescale piloting and manufacturing trial runs. At this stage, the supplier companies make the necessary equipment installations to provide appropriate quantities of raw materials for use by the detergent product manfacturers in making large experimental batches of finished products.

Both the detergent ingredients and the finished products then undergo extensive use testing and biological degradation studies by each manufacturer as a final step to full-scale manufacturing.

Insofar as the Colgate-Palmolive Co. is concerned, I am pleased to report that a very promising type of detergent is currently in the final testing stage. Although I cannot speak with specific knowledge concerning the other manufacturers, it appears that they have made similar progress. Even though testing is

still in progress, some supplier companies have made known their plans to pro ceed with preparations for commercial manufacturing.

We in my company are confident that the new material will prove successful as a replacement for the current allcyl benzene sulfonate in our products, and it appears that other detergent manufacturers are similarly confident.

STATEMENT OF HENRY V. Moss

Director of Quality of the Inorganic Chemicals Division, Monsanto Chemical Co. and Member, Technical and Materials Division Research Committee; Past Chairman of Technical Advisory Council, and Research Steering Committee, the Soap and Detergent Association

Mr. Chairman, and gentlemen, I am Henry V. Moss, an industrial chemist with Monsanto Chemical Co. in St. Louis, Mo., and past chairman of the technical advisory council and research steering committee of the Soap and Detergent Association. My position with Monsonto is director of product quality of the inorganic chemicals division which is one of the principal producers of raw materials for the detergent industry. During my 30-odd years with Monsanto I have been largely associated with various aspects of research, development, production, and quality control of products used in the manufacture of domestic and industrial detergents.

I welcome this opportunity to discuss briefly from the point of view of a supplier of raw materials to the detergent industry the activities during the last several years directed to the development of more biodegradable surfactants (the essential detergent base materials). My comments will deal primarily with activities of my own company which may be illustrative of similar efforts by other important organizations which from published information (1) (2) (5) are known to be racing toward the same goal.

Research on development of more biodegradable surfactants was initiated within Monsanto in 1956 when, as a result of cooperative industry research that has been mentioned, the ultimate need for a different detergent base material was anticipated. Monsonto's efforts have been expanded progressively since then and represent an expenditure to date of roughly $3 million. Existing Monsanto effort represents the most extensive single research undertaking presently active in the corporation and comprises assignment of 42 technical specialists full time and 8 to 10 other technologists part time, to various phases of this investigation. Present expenditures are at the rate of over $1 million a year.

This intense single effort, which we have reason to believe from published data (1) (2), is duplicated by other existing or potential producers of detergent raw materials, should adequately demonstrate sincerity of purpose by industry and refute mistaken implications that industry is apathetic. It should be recognized that industry cannot afford to make research expenditures of this magnitude as a gesture.

What actually has been done?

By way of outline, the overall project may be broken down into five stages: (1) Development of fundamental scientific information on biodegradation of surfactants.

(2) Design of a new surfactant to meet the following criteria:

(a) Be biodegradable.

(b) Raw material be available in large volume.

(c) Possess satisfactory functional and physical properties for a detergent. (d) Be economically feasible.

(3) Development of raw materials-chemistry, process, engineering, construction of manufacturing facilities.

(4) Development of surfactants-chemistry, process, engineering, construction. (5) Development of finished detergent products. This phase is one step removed from the immediate areas in which the raw material supplier is involved, but is inevitably related as factors here impinge on all the phases that precede it. The last four stages must of necessity all be under investigation concurrently since they all interact with each other. For example, the raw material originally visualized might turn out to require impossible engineering design for commercial production. Modifying engineering to make it feasible then calls on checking for the effect of this modification on the yields and various functional

properties of the product. We have something like a jigsaw puzzle with hundreds of pieces that must be fitted into the final picture and, until the picture is completed, there is no assurance that all of the necessary pieces are available. Like any other technical research investigation, the first essential steps comprised fundamental studies, involving in this case acquiring an understanding of biological processes that cause breakdown or biodegradation of materials and more particularly organic materials like alkylbenzene sulfonate (ABS). Further, to relate the biological mechanisms to the mode of attack on the molecular structure of organic substances and thereby gain knowledge of the arrangement of basic chemical groupings within various structures that are resistant and conversely those that are suspectible to breakdown-products, to be useful as detergents, must not be so loosely held together as to favor degradation by simple hydrolysis (disruption simply by water) and a structural configuration must be retained that is essential for detergency (ability to clean). Something like 450 samples have been studied in this work so far in our laboratories alone. Another area that has required much fundamental study and, I hasten to say, still requires much more study, is a satisfactory way of measuring biodegradability in a manner that portrays what actually happens in nature. Three procedures have been developed in our laboratories; these all consist in determining the amount of detergent that remains at specified intervals after addition of a known concentration of a product to a biologically active system. Development of a standard test that can be employed in any laboratory is now under collaborative investigation by a research subcommittee of the Soap & Detergent Association. We welcome cooperation in this important work by members of HEW and USPHS.

It must be realized that laboratory testing procedures are at best only an indication of what can occur in practice in the field and to assure desired behavior, performance under actual field conditions also needs to be demonstrated and correlated with results from a laboratory test if the latter is to be meaningful.

Great advances have been made in these areas and to conserve space I wish to refer those who are interested in more detail to a publication (3) by Dr. R. D. Swisher, senior group leader in our research department.

Having established insight to the structural properties required in a biodegradable detergent it follows that information must be and has been developed on means of creating the desired structure and finding suitable building blocks which even today are not commercially available in the large quantities required. This has involved worldwide investigation on our part and no doubt by others of possible sources of basic raw materials and of methods of synthesis to properly assemble the desired final complex structure.

To function as a surfactant, a material must consist of two principal parts. One must be soluble in water and is referred to as the hydrophilic end; the other must be soluble in oils or fats and is the hydrophobic or water-repelling end. It is this dual "personality" of all surfactants that makes them insinuate or orient themselves at water surfaces (hence surfactant) and between particles of soil or dirt that are attached onto solid surfaces (fabrics, dishes, the skin, etc.). A recent understandable dissertation of this subject has been given by Professor McGauhey of the University of California (4).

In ABS, the hydrophobic end consists of an elongated hydrocarbon chain known as an olefin and the hydrophilic end is a salt of benzene sulfonate to which the olefin is attached.

For optimum biodegradability, maximum linearity (straightness) of the hydrocarbon chain is desired. However, from the standpoint of performance as a detergent, branching in the chain is preferred. This is one of the complications in the jigsaw puzzle previously mentioned.

How then is the desired configuration of the chain, the starting olefin, accomplished? Much has been done here to tell us whether to build up or polymerize a simple entity like ethylene-or to break down large molecules into smaller ones by cracking-or to separate potential starting materials by solvent extraction or so-called molecular sieving prior to further processing as for example by chlorination.

These alternatives and others had to be studied individually to ascertain not only characteristics of the end product resulting fron each process but to evaluate each approach economically on its own and in relation to what might be done by competition where availability of raw materials and disposal of byproducts for which there is no known use today. Simple arithmetic shows that