Analytical Development Work for Detergent ABS Determination in Waste WatersAuthor(s): Ralph HouseSource: Sewage and Industrial Wastes, Vol. 29, No. 11 (Nov., 1957), pp. 1225-1227Published by: Water Environment FederationStable URL: http://www.jstor.org/stable/25033469 .

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ANALYTICAL DEVELOPMENT WORK FOR DETER GENT ABS DETERMINATION IN WASTE WATERS

By Ralph House

Chairman, Subcommittee for Analysis of ABS, Association of American Soap and Glycerine Producers

Formation of Analytical Committee

In 1954 the Technical Advisory Committee of the Association of Amer ican Soap and Glycerine Producers

(AASGP) formed an analytical sub committee to develop improved analyti cal procedures for detergent alkyl benzene sulfonate (ABS) in sewage and receiving waters. Representatives from several interested organizations have been associated with the work of this committee. Those organizations

which have been represented on the committee are : Atlantic Refining, Cali fornia Research Corporation, Colgate Palmolive, Continental Oil, Lever Bro

thers, Monsanto Chemical, National

Aniline, Procter and Gamble, and the U. S. Public Health Service.

Need for Improved Analytical Methods

Interest in improved analytical pro cedures for ABS arose because of com

plaints that detergents caused operat ing difficulties in sewage treatment

works and might be undesirable con taminants in surface waters. ABS is the principal active ingredient in most household detergents. These products ordinarily contain 15 to 30 per cent active ingredient, the remainder being primarily inorganic builders.

Use concentration of household de

tergents varies from about 0.1 to 0.3

per cent (1,000 to 3,000 p.p.m.) in the wash water. High dilution in the sew ers with detergent-free water gives very low concentrations at the sewage treat

ment plant. Still further dilution oc curs in receiving waters. At these low

concentrations, natural organic matter

present in sewage and surface waters

might be expected to interfere with direct colorimetric methods.

Interferences in Colorimetric Methods

The basic method for estimating ABS in trace concentrations is that of Jones (1). In this method a cationic

dye (m?thyl?ne blue) is reacted with the anionic sulfonate to form an oil soluble compound which is extracted into chloroform and measured colori

metrically. Colorimetric methods of this type

work quite well in distilled water, but serious interferences are sometimes

present in sewage and surface waters. Numerous attempts to eliminate or cor rect for interferences have been made.

Degens et al. (2) found that inter ference from nitrate and thiocyanate ions can be minimized. Edwards and

Ginn (3) titrated with a quaternary ammonium compound at pH 7.0 to 7.5 to eliminate interferences from soaps and proteins which occur in alkaline and acid solutions, respectively. This titration method is primarily of inter est at concentrations of 100 p.p.m. and

higher, and is only of limited use at the much lower concentrations to be

expected in sewage and surface waters.

Longwell and Maniece (4) eliminated

protein and soap interference by first

extracting at pH 10 and then washing with acidified m?thyl?ne blue. Moore and Kolbeson (5) used methyl green instead of m?thyl?ne blue and extracted

with benzene instead of chloroform. The nature of interferences was altered

1225

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1226 SEWAGE AND INDUSTRIAL WASTES November, 1957

by the changes, but the interferences were not eliminated.

Unfortunately proof that the effects of interferences have been eliminated can only be obtained by comparison

with results from a method of known

high accuracy or by recovery and iden tification of the ABS. In the absence of such a method, there was consider able doubt that reported results based on colorimetric methods were accurate.

Interferences from proteins and soluble

inorganic compounds can probably be

eliminated, but some naturally occur

ring organic sulfates and sulfonates

may still interfere. Positive interferences have been re

ported by Fairing and Short (6) using the direct m?thyl?ne blue procedure on

urine and aqueous extracts of straw,

manure, leaves, and rotted wood.

Hooker and others (7) found similar

positive interference in urine and

aqueous extracts of coffee, tea, straw,

and paper mill wastes using various

modifications of Jones7 method such as

those of Longwell and Maniece (4) and

Degens et al. (2). Many of the complaints about ABS

as a pollutant are based on the above

types of analytical procedures. Others are based on the appearance of froth,

which is not as reliable an indication

of the presence of detergents as is com

monly supposed. The type of froth ob

tained with ABS at a few parts per million is quite unstable and disap

pears rapidly. On the other hand,

many proteinaceous materials and

other natural products such as bile

salts are surface active and can pro

duce stable froths under some condi

tions. In light of these considerations, it is evident that less equivocal analyti cal data are needed to clarify the sit

uation.

Status of Committee Work

Referee Method for Water

Two requisites of a referee method

are: (a) complete (or reproducible) re

covery of ABS and (b) positive identi fication of the recovered material. Colorimetric methods cannot fulfill these requirements. The committee therefore agreed that its first objective

would be to develop a method to re cover ABS as quantitatively as possible from very dilute solutions, then to

purify the recovered ABS sufficiently for positive identification.

Under the chairmanship of P. J.

Weaver, Procter and Gamble Company, a referee method for ABS in water was

developed after considerable work in the laboratories of the various member

organizations. This method and the re

sults of cooperative testing of Ohio River water were presented before the American Chemical Society Summer

Symposium on Analytical Chemistry at the University of California, Los An

geles, Calif., on June 14, 1956, by a

member of the committee (8). Essen

tially 100 per cent of the ABS is de

tected using this method. The method involves adsorption of

the ABS on activated carbon, elution,

purification by acid hydrolysis and ex

tractive techniques, and final estima tion and identification by infrared spec

troscopy. The procedure is lengthy and not suited for survey work. How

ever, it satisfies the original need of a

referee method for resolving controver

sial cases and for establishing the valid

ity of shorter methods.

Referee Method for Sewage

The committee is currently investi

gating a similar method for use in sew

age. Results to date on local sewage

samples are encouraging, and it is ex

pected that cooperative tests will be

carried out on a sewage sample in the

near future. If this procedure proves

satisfactory, it will be made generally available.

Short Method

A short method for determining ABS

in sewage and surface waters is needed

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Vol. 29, No. 11 DETERGENT RESEARCH 1227

so that reliable data can be obtained in the field by sewage plant personnel and others interested in ABS concen tration levels. The committee decided that a project to develop such a method could best be carried out by an inde

pendent research organization to speed results and avoid undue work load on

committee member organizations. A number of universities and re

search institutes were contacted, and several who were interested in the prob lem submitted proposals for the proj ect. On the basis of previous experi ence and interest in similar analytical problems in the field of pharmacology, the proposal of Professor Orville H.

Miller and V. J. Patel of the University of Southern California School of Phar

macy was accepted. Work on the proj ect started in July, 1957.

When a successful short method has been developed, it is hoped that a large amount of reliable data on the ABS content of sewage and receiving wa

ters throughout the country can be ac

cumulated. When sufficient data are

available, it should be possible to clar

ify the situation regarding ABS as a

potential trouble maker in sewage

plants and water pollution.

References

1. Jones, J. H., "

General Colorimetric Method for Determination of Small

Quantities of Sulfonated or Sulfated Surface Active Compounds.'9 Assoc.

Official Agr. Chemists, 28, 398 (1945). 2. Degens, P. N., Evans, H. C, Kommer, J.

D., and Winsor, P. A., "

Determina tion of Sulphate and Sulphonate

Anion-Active Detergents in Sewage.'' Jour. Appl. Chem., 3, 2, 54 (Feb., 1953).

3. Edwards, G. P., and Ginn, M. E., "De termination of Synthetic Detergents in

Sewage." This Journal, 26, 8, 945

(Aug., 1954). 4. Longwell, J., and Manieee, W. D.,

" De

termination of Anionic Detergents in

Sewage, Sewage Effluents and River Waters." Analyst, 80, 167 (Mar., 1955).

5. Moore, W. A., and Kolbeson, R. A., "De termination of Anionic Detergents in

Surface Waters and Sewage with

Methyl Green." Anal Chem., 28, 2, 161 (Feb., 1956).

6. Fairing, J. D., and Short, F. R., "Spee trophotometric Determination of Al

ky lbenzenesulfonate Detergents in Surface Water and Sewage." Anal.

Chem., 28, 12, 1827 (Dec, 1956). 7. Hooker, D. T., Sallee, E. M., and Weaver,

P. J., Unpublished data, Procter and Gamble Co. (1955).

8. Sallee, E. M., et al., "Determination of Trace Amounts of Alkylbenzenesulfo nates in Water." Anal. Chem., 28, 12, 1822 (Dec, 1956).

MEMBERSHIP DIRECTORY

The biennial complete directory of Federation membership for the 1957 calendar year will be a featured part of the March, 1958, issue of This Journal.

Be certain that your listing is up-to-date. Turn to page 1251 of this issue for full information.

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