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Development of MSDS - Material Safety Data Sheet

Development of Material Safety Data Sheets

Presented at the 191st ACS National Meeting
13-18 April 1986; New York, NY
Samuel Aaron Kaplan
Division of Chemical Health and Safety

Material safety data sheets contain written or printed material concerning a hazardous chemical as prescribed by law. They contain basic information needed to insure the safety and health of the user at all stages of its manufacture, storage, use, and disposal. They developed out of the chemical data sheets that chemists have been using for the past one hundred or more years. But,they have a long and interesting history, extending back into time and climaxing into the present day format.

The history of the material safety data sheets (MSDS) can be presented in many ways. I have chosen to show its development in a logical, historical sequence. In order to do this, I have rearranged its format as it developed over time.

The earliest mention of some of the requirements covered in the MSDS goes back into the dawn of time when information was exchanged verbally on the materials used as medicines and for dyes. This required the random testing of the natural materials available to man at that time. Through trial and error, man, that creative creature he is, gradually built up a large body of knowledge concerning the preparation of simple drugs and dyes, their storage parameters, application and hazards of use. This information forms the basis of a chemical data sheet.

The earliest written material has been found in the tombs of the Egyptians, either on the walls of their tombs or on papyrus records. These date back over 4,000 years and include the prescriptions of Imhotep, the first great Egyptian physician. This data while basically a pharmaceutical description of the materials used in the treatment of the various diseases prevalent also included the sources, names, preparation, storage and application procedures, as well as warnings against improper use and application.

Within a few hundred years or so, the early Sumarians, in the land between the two great rivers, developed the cuneiform system of writing, which has been preserved for us on clay tablets. They extended the knowledge of the Egyptians and added many more materials to this body of knowledge, especially in the area of dyes.

A thousand or so years later, the Greeks began to record not only their own observations, but also some of their early experimental work. The recordings of Herophilus and others added to our growing knowledge of natural chemicals of daily use. During the great blossoming of medical inquiry, in the fourth and third centuries B.C. at Alexandria, real experimentation into new drugs, dyes, bleaches, and other organic and inorganic materials occurred.

During the Roman period, there was an increase in the supply of pharmaceuticals available to the physician due to the large army required to maintain the Roman Empire. Much of this work was recorded by Galen in his works on medicine and the human body.

During the so called Dark Ages, the period between the fifth through about the fourteenth centuries, much of the work of the previous centuries was maintained in the monasteries of Europe, though not in its entirety. The bulk of the knowledge of the Near East, Greece and Rome was preserved and expanded by the Islamic nations, especially during their great renaissance of the ninth, tenth, and eleventh centuries. Much of this work was done and recorded in Alexandria and Baghdad. This material included, for the first time, some of the formulations of China, India and the Far East.

By the end of the fourteenth century, much of this knowledge had been transferred to the southern parts of Italy and France and led to the European Renaissance, which brought about a resurgence of inquiry into the very nature of the materials used today.

Up to this time every idea, formula, etc. had to be copied by hand, restricting the widespread use of "Chemical Data Sheets." With the advent of movable type toward the end of the fifteenth century, the emergence of the modern chemical data sheet grew near. It had to await the development of standard units of measurement which would be accepted by the growing scientific community. Though this did not occur for two hundred years or so, some material was printed concerning chemical hazards.

It is highly probable, though difficult to prove, that some of the more enlightened manufacturers of pharmaceuticals and dyes did pass on some of their precautions and methods of handling to their customers. This can be inferred from some of the letters written by the chemists of this time. Most of the information which would have been on these early chemical data sheets would have related to methods of handling, storage and possibility of some inherent danger.

It is safe to assume, from all the information I can gather, that by the middle of the nineteenth century, manufacturers where supplying their customers with some sort of data sheet, either along with their product or on demand. Therefore, the parameters of the MSDS, Sections 1, 3, an 9, had been dealt with by this time. The earliest example of an MSDS that I have ever seen is one by Valentine and Company of 1906. I came across this example while doing a research paper for NIOSH in 1980.

What makes this period difficult to reconstruct are two factors: A) The habit of chemists to dispose of older copies of chemical data sheets when a new one appears; and B) Where information does exist in manufacturers files of early data sheets they seem reluctant to part with it. As one of my sources told me, the legal department objected to its release, fearing a possible liability suit. Why, he wasn't sure.

By the middle of the nineteenth century, chemists had developed flash points and freezing points for various materials. Over the next sixty or more years, with the increasing interest of the insurance industry, the infant fire fighting companies, which developed in the cities, and the newly founded National Fire Protection Association (NFPA), more and more chemists were involved in the development of the test of the parameters covered in Section 4. By the early nineteen thirties, reactivity data, Section 6, had been added to the literature. Most of this work was prepared in the laboratories of the companies developing new chemicals, some in the laboratories of the Bureau of Standards and other government agencies, while some were consensus standards produced by NFPA, the American Standard Association and similar groups.

Health hazard data, much of which was developed over the past five to six thousand years or more, was enhanced within the past one hundred and fifty years. Started originally in Europe, and within a few years in the United States, work proceeded on the development of a body of literature covering the toxicity of chemicals to animals and man. Some of this early work was done at the United States Public Health Laboratory in downtown Washington, while other research was done at Johns Hopkins in Baltimore and other great medical institutions of that time. Among those working in this field were Dr. Alice Hamilton, Charles Wardell Stiles, Drs. Henderson, Haggard, M.B. Jacobs, Tulipan, etc. Thus, the work that went into the development of the effects of overexposure, etc. became part of Section 5.

The threshold limit values were developed out of the early work of the industrial hygienists and toxicologists of the industrial states. Originally called Maximum Allowable Concentrations, they varied from state to state. They were compiled, in about 1947 by an insurance industrial hygienist, Mr. Warren Cook.

In 1938, the NCGIH's (National Conference of Governmental Industrial Hygienists) started to issue a consensus listing, "Maximum Allowable Concentrations" (MAC). In approximately 1958 - 1959, these were changed to "Threshold Limit Value" (TLV). With the adoption by OSHA of these values, they became "Time Weighted Averages" (TWA). The rest of the Section grew out of the work on health.

The Section on emergency and first aid procedures is also as old as time. These requirements, listed under Section 7, developed over the years in response to problems arising in the production of a particular chemical. It was only fitting, in order to retain the good will of it's customers, that this information was added to the chemical data sheets being supplied to them. Through the years, elaborate procedures have been developed by chemical companies for emergencies. At the same time, insurance companies, NFPA, the Chemical Manufacturers Association (CMA), and the Department of Transportation have been developing standards, and in DOT's case, required procedures to be followed in the event of an emergency/accident. One of the fastest emergency response sources of information is that maintained by CMA.

In essence, the last two sections, 8 and 2, are of fairly recent origin. The special protection requirements, listed in 8, have gradually developed in response to a particular hazard. Gloves, mitts, pads or what have you were used to protect the hands from heat and very sharp objects. They are the oldest form of body protection devices developed by man. Some sort of respiratory protection was in use over two thousand years ago for dusty atmospheres. These methods, mostly an animal bladder and later a damp cloth covering the mouth and nose, were the only respiratory protective device used until World War I. The use of war gases led to the rapid development of the first gas masks, using charcoal and other materials as absorbants and inertants. After the Great War, chemical companies, realizing the value of gas masks, adapted them for emergency use. Today, the throw-away masks are in essence a return to the old "wet rag" form of respiratory protection, though more highly developed for use in low hazard areas. Clothing is also an old form of body protection.

The two most recent forms of protective equipment are eye protective devices and the use of ventilation. Eye protection has developed as we know it mainly within the past fifty years or so. This came about when skilled labor began to be too expensive to replace. The lens manufacturers have developed many forms of eye protection, some specifically tailored to special industrial operations.

Natural ventilation has always existed and had been the only form of ventilation until the industrial revolution. Before electricity, during the late nineteenth century, some plants were mechanically ventilated by fans running off of jack shafts powered by water or steam. The development of electric fans brought some relief into the work place. In the early part of this century, a centralized form of general ventilation began to be developed. At the same time, local exhaust ventilation as we know it started to make inroads on the industrial scene. By World War II, ventilation, general and local, was being used to an increasing extent by the chemical industry.

Section 2 of the MSDS was the last Section developed, and is the result of the Department of Labor's response to incidents occurring in the shipbuilding industry. The hazards discussed within this Section, i.e.: hazardous mixtures and ingredients - effect only a few industries, specifically the protective coating/paint industry.

Up to this point, we have discussed the history of the development of the various factors making up the MSDS. This has been done in order to show that nothing exists in a vacuum. What may appear to be a simple act, was based on thousands of years of development. By the late nineteen fifties, thousands of chemical data sheets were in use by chemists throughout the world. These were supplied to the customer by the manufacturer. They came in many forms, some were single sheets of pertinent information while others were elaborate bound volumes supplied gratis to the customer.

These chemical reports, covering specific chemical products, ranged from chemical data sheets produced for their own internal use or by their customers to very detailed documents publicizing their products. Internal reports covered methods of production, hazards and control, disposal, maintenance and emergency procedures.

Right after World War II, the Department of Labor began to publish a series of documents under the title, "Controlling Chemical Hazards." The first, "Ammonia", was published in 1945 and then reprinted in 1955. They published these documents in order to act as a source of information for the worker in chemical plants. Similarly, various industrial states were publishing chemical hazard guidelines. About the same time, the Manufacturers Chemical Association (the current CMA) began to publish their "Chemical Safety Data Sheets", starting with "Formaldehyde" in 1946. This was their famous "SD" series of publications. They were extensive in their coverage of a particular chemical. These are no longer published for fear of a product liability or related suit. In 1949, responding to the needs of their field engineers and underwriters, the American Association of Casualty and Safety Companies began to publish a series of "Special Hazard Bulletins", and in 1951, "Chemical Hazard Bulletins." These were distributed mainly to their insureds, both large and small chemical companies and end users of hazardous chemicals.

By the end of the nineteen fifties, when Congress passed the "Longshoremans and Harbor Workers Act of 1958", Public Law 85-742, all of the elements found in the MSDS had been developed, with the possible exception of Section 2. With the passage of the Act, the DOL set up a separate office of maritime safety. Ralph W. Netterstrom was appointed Division Chief to head this section. He hired safety oriented personnel including: Joseph LaRocca, Assistant Chief, Shipyard Branch; and Edward C. March, Assistant Chief, Longshore Branch to look into the problems affecting maritime and dock workers. A series of incidents over the next few years indicated the source of many of the accidents in this area were chemically related.

In the mid nineteen sixties, Dr. Van Atta (an industrial hygienist) was hired as the head of the Industrial Safety and Occupational Health Support Office, and thus provided assistance to Mr. LaRocca's group. Based on the recurring chemically related problems within his jurisdiction, Mr. LaRocca and his group investigated the types of chemical data sheets used by industry. I recall that late in 1967 while working for the American Insurance Association, I received a request from his department to send them copies of our chemical hazard publications.

Working over a period of a year or more, his group produced a document called "Material Safety Data Sheet", which included Form No. LSB-OOS-4. This is the original governmental MSDS. This form, in order to meet the needs of maritime workers, added for the first time to a chemical safety sheet the items listed in Section 2. This format was limited by law to the ship building, breaking and repairing operations. It was published on August 23, 1968 in 33 FR 12008 as amendments to 29 CFR parts 1501, 1502 and 1503. This amendment went into effect approximately 180 days after publication.

During this period, there was pressure on Congress to extend benefits of the Longshoremans Act, plus additional safety and health coverages, to all of the nation's industrial workers. With the passage of Public Law 91-596, on December 29, 1970, OSHA was established within the DOL. Among one of its first acts, it incorporated within itself as a separate section, most of the maritime regulations. Form LSB-OOS-4 became Form OSHA-20 and was issued as revised May, 1972.

Over the years, there has been pressure on OSHA to issue either Form 20 or some similar format as part of their overall regulatory requirements. This discussion, which covered a period of 8 - 10 years, resulted in OSHA issuing preliminary statements of intent between 1975 and 1982. Having been involved as a consultant working for OSHA in 1977, I can state that the debate within OSHA for issuing a ruling was very intense.

Finally, on Friday, November 25, 1983, in Rules and Regulations of the Federal Register, Volume 48, Number 228, OSHA issued its final regulations. Under this ruling, MSDS's (either an improved form Number 20 or some similar format) were required for all shipments of hazardous chemicals leaving the manufacturers work place and from all importers of such on all shipments by November, 1985. Distributors and employers were to comply as of that same date. All employers will be in compliance with all provisions of this section including initial training requirements for all current employees by May 25, 1986.

The Act, for all intents and purposes, is in effect at this moment. The MSDS form was put together from existing formats published by various chemical companies, State regulations, and associations. It was tailored to meet the needs of a specific area of industrial uses. With all its failings, it does include the main areas of concern of safety and health professionals while filling the needs of the working chemist, the end user, and above all, the industrial worker.


  • "Chemical Hazards Bulletins", C-Series, American Insurance Association, New York, New York, 1951 on.
  • "Chemical Safety Data Sheet", SD-Series, Chemical Manufacturing Association, Washington, D.C., 1946 on.
  • "Chlorine", Bulletin 125, Hooker Electrochemical Company, Niagara Falls, New York, 1952.
  • "Controlling Chemical Hazards", A series of chemical hazard bulletins published by the Bureau of Labor Standards, U.S. Department of Labor, Washington, D.C., 1945 - 1960.
  • Darrow, Floyd, L., "The Story of Chemistry", The Chautauqua Press, Chautauqua, New York, 1928.
  • "Ethyl Alcohol Handbook", U.S. Industrial Chemicals Co., Division of National Distillers and Chemical Corporation, New York, New York, 1960.
  • "Material Safety Data Sheet", product of the Linde Division, Union Carbide Corporation, Danbury, Connecticut, 1985 on.
  • "Material Safety Data Sheet", U.S. Department of Labor, Washington, D.C., 1970, (U.S. Printing Office: 1970-0-402-661).
  • Public Health Bulletins Nos. 71, 106, 225, Division of Industrial Hygiene, National Institute of Health, Washington, D.C. 1915, 1920, 1940.
  • Rankin, S.L., M.D., "Regulations Governing the Handling and Blending of DuPont Tetraethyl Lead Compounds", Petroleum Chemicals Division, E.I. du Pont de Nemours and Company (Inc.), Wilmington, Delaware, September 1, 1947.
  • "Safety in the Use of Benzene (Benzol)", The Barrett Division, Allied Chemical and Dye Corporation, New York, New York, 1942.
  • Singer, Charles, S., "A Short History of Scientific Ideas to 1900", Oxford University Press, New York, New York, 1959.
  • "The Thomas Registry of Manufacturers", New York, New York, Publications of 1900 - 1910 (published yearly since 1900).
  • "The Hidden Hazards", A film produced by the U.S. Public Health Service in 1959 - 1961 (No longer available).
  • "The Human Body", A series published by Torstar Books, New York, New York, 1985.
  • "Zinc Oxide - Rediscovered", The New Jersey Zinc Company, New York, New York, 1957.
  • Individual telephone conversations with: Dr. Dan Marsick, Max Gabis, Tom Seymour, Joe Young (retired) - OSHA; Milton Freifeld (retired) - CMA; Newell E. Bolton - Union Carbide; various members of the American Chemical Society's History of Chemistry Section; Ollie White - General Electric and others too numerous to mention.


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