68
Scholars' Mine Scholars' Mine Masters Theses Student Theses and Dissertations 1966 Some effects of selected biodegradable detergents on the Some effects of selected biodegradable detergents on the aeration of water and activated sludge aeration of water and activated sludge Donald Ernest Modesitt Follow this and additional works at: https://scholarsmine.mst.edu/masters_theses Part of the Civil Engineering Commons Department: Department: Recommended Citation Recommended Citation Modesitt, Donald Ernest, "Some effects of selected biodegradable detergents on the aeration of water and activated sludge" (1966). Masters Theses. 5770. https://scholarsmine.mst.edu/masters_theses/5770 This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected].

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Page 1: Some effects of selected biodegradable detergents on the

Scholars' Mine Scholars' Mine

Masters Theses Student Theses and Dissertations

1966

Some effects of selected biodegradable detergents on the Some effects of selected biodegradable detergents on the

aeration of water and activated sludge aeration of water and activated sludge

Donald Ernest Modesitt

Follow this and additional works at: https://scholarsmine.mst.edu/masters_theses

Part of the Civil Engineering Commons

Department: Department:

Recommended Citation Recommended Citation Modesitt, Donald Ernest, "Some effects of selected biodegradable detergents on the aeration of water and activated sludge" (1966). Masters Theses. 5770. https://scholarsmine.mst.edu/masters_theses/5770

This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected].

Page 2: Some effects of selected biodegradable detergents on the

SOME EFFECTS OF SELECTED BIODEGRADABLE DETERGENTS ON THE AERATION OF WATER AND ACTIVATED SLUDGE

BY

DONALD ERNEST MODESITT

A

THESIS

submitted to the faculty of

THE UNIVERSITY OF MISSOURI AT ROLLA

in partial fulfillment of the requirements for the

Degree of

MASTER OF SCIENCE IN CIVIL ENGINEERING

Rolla, Missouri

1966

Approved by

'•

Page 3: Some effects of selected biodegradable detergents on the

ABSTRACT

The purpose of this study was to determine what effects the

presence of selected biodegradable detergents have on the aeration of

water and the activated sludge process for aerobic wastewater treat­

ment. The detergents studied were LAS #1, Alfol, and Nalkylene. It

was of particular interest to determine if these detergents decreased

the oxygen absorptive capacities of water and wastewater. If detri­

mental effects were produced by the detergents it was then desired to

determine if these effects were serious enough to create problems with

aerobic wastewater treatment and aeration in receiving bodies of

water.

A two liter volume of the liquids were aerated by bubble aeration

at rates of 300 and 600 ml/min/1. The effects produced by the presence

of 2, 5, and 10 mg/1 of each detergent on the rate of oxygen transfer

and oxygen saturation concentration of distilled water, tap water, and

activated sludge were compared with the effects exhibited by similar

aeration of the same volume of liquid without the presence of detergent.

It was found that each detergent did not produce the same degree

of effect in the different liquids. It was found to be possible for a

detergent to decrease the oxygen transfer rate and oxygen absorptive

capacity in distilled water and tap water yet increase the oxygen

transfer rate and oxygen absorptive capacity of the activated sludge

over that which existed when the detergent was not present.

The degree of effect produced by the detergents was not always

proportional to the concentration of detergent. The rate of aeration

was noted to be capable of causing a change in the effects produced by

the detergents.

Page 4: Some effects of selected biodegradable detergents on the

ACKNOWLEDGMENTS

The author expresses his appreciation for the enthusiastic

assistance of Dr. Don F. Kincannon throughout the study and in the

preparation of this thesis. He is also thankful to Professor J. Kent

Roberts for his helpful suggestions.

The author wishes particularly to acknowledge his wife for her

patience, encouragement, and helpfulness while this thesis was in

preparation.

Acknowledgment is also made to Mr. Theodore E. Brenner, Research

Director of the Soap and Detergent Association, and Dr. James C. Kirk

of the Continental Oil Company for the detergent samples and

information they courteously provided.

Page 5: Some effects of selected biodegradable detergents on the

TABLE OF CONTENTS

PAGE

LIST OF FIGURES • • . • . • . • • • • . • • • • • • . • . • . • • . . . • . • . • • • . • • • . • . • • . . • . . . . i i

I.

II.

III.

IV.

v.

VI.

VII.

VIII.

INTRODUCTION .•••••••••.•.••.•.••••.•••..••.•.••....•••••••.

REVIE'W' OF LITERATURE .•••••.••..••.•.•••••.••••.•••••.•••••.

THEORETICAL CONCEPTS ••••••..•••..••••..•••••••••.•••.••••••

MATERIALS AND METHODS .•••••• A. B.

Materials •••••• Methods .•••••••

. ...... .

PRESENTATION OF RESULTS •••• A. Distilled Water System. B. Tap Water System .•••••• C. Activated Sludge System •••••

DISCUSSION OF RESULTS .••••••• A. Distilled Water System ••• B. Tap Water System •••••.•••••••• C. Activated Sludge System ••••••• D. Overall Oxygen Transfer Coefficient, ~a

CONCLUSIONS ••••••••••••••.•••..•..••..••••.••.•••••••••••••

REC~NDATI ONS .•••••••••••••••••••••.••••••••••.••••••••••

1

4

8

14 14 16

23 23 28 36

48 48 49 50 51

56

58

BIBLIOO.RAPIIY.... • • • . • • • • • • • • • • . • • • • • • • . • . • • • • • • • . • • • • • . • • • . 59

VITA....................................................... 61

Page 6: Some effects of selected biodegradable detergents on the

ii

LIST OF FIGURES

FIGURE PAGE

1. Concentration of Oxygen in Water vs. Time •••••••••••••.••••. 9

2. Absorption of Oxygen in Water ••••••••••••••••••••••••••••••• 10

3. Experimental Equipment .••.••••.••..•.....•••••.•.•••....•... 17

4. Activated Sludge Units .•••.•••.••••••...•.••.••..••••••••••. 20

5. Optical Density vs. Biological Sbl{da ::: •••••••••••••••••••••• 21

6. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Distilled Water Containing LAS #1 •••••••••.••••• 25

7. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Distilled Water Containing Alfol •••••••••••••••• 26

8. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Distilled Water Containing Nalkylene •••••••••••• 27

9. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Distilled Water Containing LAS #1 •••••.••••••••• 29

10. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Distilled Water Containing Alfol .••••••••••••••. 30

11. Dissolved Oxygen Deficit vs. Time for 600 ml/mintl Aeration of Distilled Water Containing Nalkylene .••••••••••• 31

12. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Tap Water Containing LAS #1 .•••••••••••••••••••• 33

13. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Tap Water Containing Alfol •••••••••••••••••••••• 34

14. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Tap Water Containing Nalkylene •••••••••••••••••• 35

15. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Tap Water Containing LAS #1 •••••••••••••••.•.•.. 37

16. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Tap Water Containing Alfol .••••••••••••••••••••• 38

17. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Tap Water Containing Nalkylene •••••••••••••••••• 39

18. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Activated Sludge Containing LAS #1 .••••••••••••• 42

Page 7: Some effects of selected biodegradable detergents on the

iii

LIST OF FIGURES (Continued)

FIGURE PAGE

19. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Activated Sludge Containing LAS #1 •••••••••••••• 43

20. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Activated Sludge Containing Alfol ••••••••••••••• 44

21. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Activated Sludge Containing Alfol ••••••••••••••• 45

22. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Activated Sludge Containing Nalkylene .•••••••••• 46

23. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Activated Sludge Containing Nalkylene .•••••••••• 47

24. ~a vs. Detergent Concentration in Distilled Water ••.••••••• 53

25. ~a vs. Detergent Concentration in Tap Water ...•...•.•...... 54

26. ~a vs. Detergent Concentration in Activated Sludge ••••••••• 55

Page 8: Some effects of selected biodegradable detergents on the

I • INTRODUCTION

With the increase in water reuse and increasing quantity of

synthetic detergents used for residential, commercial, and industrial

purposes in recent years it should have been apparent that unless the

detergents were removed in waste treatment processes, degraded in the

receiving bodies of water, or removed in water treatment facilities

that an increasing concentration of these detergents would result in

taste, odor, and foaming problems. Anticipation of such problems did

occur to many and at least one synthetic detergent manufactur~r started

formulating plans for a biodegradable synthetic detergent as early as

1952.

In the late 1950's and into 1965 several instances of taste,

odor, and foaming problems associated with the "hard" or low­

biodegradable detergents were brought to the public's attention.

Likely there were numerous other unreported occasions when these

problems caused concern at the local level. One of the more notable

cases in point occurred in the fall and winter of 1956-57 at Chanute,

Kansas when the climatic period of a five year drought caused the city

to resort to recirculation of its sewage treatment plant effluent. At

all times during the six month period that this practice was followed

the finished water from the water treatment plant maintained a coliform

bacteria concentration below the limit recommended by the United States

Public Health Service. The detergent concentration, however, increased

to a point where at the end of the drought approximately 5 mg/1 of

anionic surfactants were contained in the drinking water resulting in

taste, odor, and foaming problems. Other cases on record with the

USPHS show up to 2.6 mg/1 and up to 5 mg/1 of anionic surfactants in

Page 9: Some effects of selected biodegradable detergents on the

well and river waters respectively. Since the 1962 Public Health

Service Drinking Water Standards set a recommended upper limit of 0.5

mg/1 of alkyl benzene sulfonate (ABS), an anionic surfactant, the need

for highly degradable detergents is well established.

At the end of 1964 the Soap and Detergent Association announced

that by mid-1965 the suppliers of basic linear alkyl sulfonate (LAS)

materials would reach sufficient volume production to enable the

manufacturers of the surfactants to change to the more biologically

degradable, or "soft", detergents. Thus in recent months as the old

rrhardn detergents have been phased out and the new more bio-degradable

''softn detergents have been put into use the reported occurances of

former detergent problems of taste, odor, and foaming have decreased.

Sawyer has noted (1) that a number of reports in the literature

indicate an increase in air (oxygen) requirements in the activated

sludge treatment of sewage since the advent of synthetic detergents.

These detergents were of the biologically "hard" type.

Sufficient oxygen must be provided in an aerobic biological waste

treatment process to meet the respiration requirements of the micro­

organisms oxidizing the organic matter in the wastewater. It there­

fore is of value to know if the new detergents significantly affect

the rate of transfer of the oxygen from the air bubbles to the liquid,

and consequently the microorganisms, in the aeration process.

The purpose of this study was to determine the effect of selected

"sofe' detergents on oxygen transfer by bubble aeration in distilled

water, tap water, and a synthetic activated sludge. Comparison

between the effect of detergents, concentrations of detergent,

2

aeration rates, and liquid systems were made. Depending upon the nature

Page 10: Some effects of selected biodegradable detergents on the

3

and degree of the observed effects it was thought some changes in

aeration design criteria for wastewater treatment might be recommended.

Page 11: Some effects of selected biodegradable detergents on the

II. REVIEW OF LITERATURE

In 1962 McKinney (2) stated, "One of the most controversial

subjects today [in waste treatmen~ is the effect of synthetic deter­

gents on oxygen transfer. There is no doubt that the presence of

synthetic detergents in pure water has an effect on oxygen transfer,

but there is reason to believe that the presence of synthetic

detergents in sewage does not depress the rate of oxygen transfer any

more than other organic components of sewage. It is strange indeed

with all the research on syndets and oxygen transfer that no one has

ever undertaken a thorough study of sewage since all the data are

aimed at sewage purification plants."

4

Maney and Okun (3) showed by a survey of literature that surface

active agents (SAA) do affect oxygen transfer in waste treatment

processes and in laboratory and pilot plant studies. The reports,

however, fail to agree upon the nature of the effect and its extent.

Some researchers report that SAA cause a decrease in oxygen transfer

rate while others report an increase and a few conclude that SAA have

no effect on oxygen transfer rate in aeration systems. The conclusions

reported in these studies undoubtedly were dependent on factors such as

the nature and concentration of SAA, the liquid phase of the system,

and the type of aeration system. For example, Holroyd and Parker (4)

found that SAA interfered greatly with oxygen transfer in bubble

aeration but hardly at all with surface aeration under stagnant con­

ditions. Maney and Okun (3) found that concentrations of sodium

dioctyl sulfosuccinate (Aerosol O.T.), a nonionic syndet, as low as

0.01 mg/1 caused changes in the physiochemical properties of the water

surface accompanied by increased resistance to oxygen transfer. Mixing

Page 12: Some effects of selected biodegradable detergents on the

5

conditions affected resistance to oxygen transfer. At turbulent flow

mixing conditions in the magnetically stirred aeration cells, oxygen

transfer was dependent mainly on surface renewal and under these

conditions the SAA had no apparent effect on oxygen transfer. The

greatest effects were observed at mixing Reynolds Numbers in the

3 3 approximate range of 5 x 10 to 15 x 10 .

Maney and Okun (5) in studies on bubble aeration showed that the

presence of SAA reduces the absolute oxygen transfer coefficient(~),

while the overall rate constant (~a) may be increased. This will occur

if the interfacial area between the air and liquid is significantly

increased by the presence of SAA thereby allowing the gain in area to

more than compensate for the inhibitory effect.

Lynch and Sawyer (6) (7), in studies on eleven syndets purchased

on the retail market, found that in concentrations of 50 mg/1 as

marketed most reduced the oxygen transfer efficiency in tap water to

varying degrees. Speculation was made as to the difficulty of

maintaining aerobic conditions in waste treatment. It appeared possible

that certain syndets could cause difficulty in maintaining aerobic

conditions in the waste treatment plant. Syndets which are not degraded

or removed in the treatment plant may be capable of reducing the

reaeration rate of receiving bodies of water to varying degrees. The

effects of the detergents may last for long distances downstream

because of their biological stability and the fact that they are not

easily precipitated.

Sawyer (1) concluded that in general all surfactants decrease the

rate at which oxygen transfer occurs from the gaseous phase to the

liquid phase. Regarding the effects of SAA on the rate of reaeration

Page 13: Some effects of selected biodegradable detergents on the

of receiving bodies of water, it was concluded that SAA residuals from

waste treatment will have little if any effect in lakes and will vary

in rivers and streams, increasing in magnitude as the degree of

turbulence increases.

6

Manganelli (8) reported that a concentration of 50 mg/1 of Naconol

N.R. (an anionic surfactant) did not hamper absorption of oxygen in

distilled water under quiescent conditions, However, in bubble aeration

approximately a 20 percent reduction in the concentration of oxygen

at saturation occurred as compared to the oxygen concentration at

saturation for the control.

Zieminski, Goodwin, and Hill (9) investigated the possibility of

improving the efficiency of aeration by the addition of small quanti­

ties of certain organic substances to the aerated liquid. Alcohols,

carboxylic acids, esters, keytones, and some commercial SAA were used.

The alcohols and carboxylic acids showed a definite increase in the

rate of oxygen transfer which increased progressively with the length

of the carbon chain. The substances which were found to be the most

effective in increasing the efficiency of oxygen absorption over that

of the control were 4-methyl-2 pentanol and isoamyl acetate. The

presence of 4-methyl-2 pentanol produced increases in the efficiency

of oxygen absorption by 50 and 100 percent for concentrations of 3.0

and 6.0 mg/1 respectively.

Eckenfelder and Barnhart (10) found the liquid film coefficient,

~, and the overall transfer coefficient, ~a' to show an initial rapid

decrease followed by a constant value or slight increase with increasing

concentration of surfactant in liquids containing concentrations up to

75 mg/1 of the surfactant, sodium lauryl sulfate. The maximum decrease

Page 14: Some effects of selected biodegradable detergents on the

7

in~ occurred over the range of maximum surface tension change. They

found that the mean diameter of the air bubbles decreased with increasing

concentration of the SAA. The increase in ~a was determined to be re­

lated to both the increase in ~ and the increase in interfacial area

for transfer per volume of liquid under aeration, A/V.

No information was found concerning the effects on oxygen transfer

caused by the new biodegradable detergents studied in this thesis or

other biodegradable detergents in general as to their effects on oxygen

transfer in the activated sludge process of waste treatment.

Page 15: Some effects of selected biodegradable detergents on the

8

III. THEORETICAL CONCEPTS

Haney (11) and others have shown that the absorption of oxygen by

a liquid under aeration conditions follows a scheme as illustrated in

Figure 1. It may be seen from Figure 1 that the rate of approach to

the saturation concentration or equilibrium condition is dependent upon

the difference between the saturation concentration, S, and the

concentration at any time, Ct. This difference, S-Ct, is called the

driving force. The driving force and rate of approach to saturation

are greater the further the system is from equilibrium.

One of the important factors affecting this rate of approach to

saturation is the formation of films at the water-air surface

(interface) which offer resistance to gas transfer (11)~ see Figure 2.

The resistance encountered by the diffusing gas molecules is due to

their collisions with the molecules in the gas and water films.

Resistance to diffusion will be greatest in the water film as the

molecules are closer together in this film. Resistance is also a

function of thickness and the gas film will probably be somewhat

thicker than the liquid film because, under comparable conditions of

turbulence, the film thickness is determined by the kinematic

viscosity, which is greater for gases than liquids (12). Although of

greater thickness, the gas film offers less diffusion resistance to

slightly soluble gases, such as oxygen, than does the liquid film.

The less soluble gases are slowly diffused across the liquid film,

therefore requiring only a small concentration difference across the

gas film. The liquid at the interface will be substantially saturated

with gas solute at the partial pressure (P) of the gas. For slightly g

Page 16: Some effects of selected biodegradable detergents on the

~ Q) bO :>,

8 4-1 0

~ 0 bO ·~ ~ .j.J ·~ ell (/) 1-4 ell .j.J Q) ~ 1-4 Q) CJ CJ ~ ~H 0 u

s T----------T ........

.j.J

u

.j.J

u

C/)

0 L---------------~----------------------------~--0 Time (t)

Figure 1. Concentration of Oxygen in Water vs. Time

9

Page 17: Some effects of selected biodegradable detergents on the

Air (mixed)

Gas Film

Water (mixed)

10

Concentration Gradjent

I

I I

~ < S C~( SX I s · (S) ~~----~~--~----~~.---~-----L----~----~--~~.---a-suratlon

Increasing Concentration

(Arbitrary Dissolved Oxygen Concentration Scale)

Figure 2. Absorption of Oxygen in Water

Page 18: Some effects of selected biodegradable detergents on the

11

soluble gases like oxygen the gas film will be considered no further in

the calculations.

The fundamental gas absorption equation applicable to. oxygen in

water according to Lewis and Whitman (12) is:

.!~ A (dt)

= - P.)··························· 1. l.

w = weight of solute dissolved (mg)

t = time (hr)

dw -- = rate of gas absorption (mg/hr) dt

A = the area of the gas-liquid interface (sq em)

k = the transfer coefficient through the gas, film (mg/sq em/ g hr/atm)

~ = the transfer coefficient through the liquid film (cm/hr)

p = the concentration of solute in the gas (atm)

C = the concentration of solute in the liquid (mg/1)

subscripts i, g, L apply to conditions at the interface, the main body of gas, and in the liquid, respectively.

Note: This equation and others to be considered will apply for conditions

of constant temperature and pressure.

At the true interface P. is in equilibrium with C .• Therefore, l. l.

C. = f(P.), and this function is the solubility relationship given by l. l.

Henry's Law: S=HP .••..••..••.•........••••••••••.............• 2.

Where: S = the concentration of the gas in the water at equilibrium

P = the partial pressure of the particular gas in the air which is in contact with the liquid

H =Henry's Law solubility coefficient

As shown in Figure 2, there is practically no concentration gradient

in the gas film, therefore, P. = P and C. = HP . l. g l. g

Page 19: Some effects of selected biodegradable detergents on the

For negligible gas film resistance, ~ = ~· ~represents the

overall gas transfer coefficient (combination of both films).

Equation 1 may then be rewritten as:

or:

C. represents the equilibrium concentration in the liquid at the ~

gas partial pressure, P , for any given temperature. g

12

By revising the nomenclature of Equation 1 and dividing both sides

by the volume of water, V, liters:

.!. ~) - (A) -V (dt) - ~ (V) (S Ct)

w As V represents the solute concentration in mg/1, this equation may be

rewritten as=

3.

in which S is the saturation concentration (mg/1) of the gas in the

water and Ct is the concentration (mg/1) of gas in the water at time, t.

d c The value ____ t represents an instantaneous rate and is not dt

applicable to any appreciable time period because of the changing value

of (S-Ct) as gas transfer occurs. See Figure 1.

Concentration changes for a given time may be found by integrating

Equation 3 between the limits of zero and t for "time" and between C 0

and C for "concentration." C corresponds to the initial concentration, t 0

or C = C when t = 0.) t 0

Page 20: Some effects of selected biodegradable detergents on the

13

d c ~

(~) t = S-C (V) dt

t

cJct -d c ~ (A) Jt t =

s-c (V) dt t

log e s-et =-K_ (A)

S -C -L (V) t . • • • • • • • •• • •• • . • • • •• • • •• • ••• • • • . 4.

~

or s-c t =- ~

s-co; ~2;:;;..,.3_0_3

For a situation where ~~~ is constant Equation 4 may be reduced to:

log e

s-et = - K_a -L t . • • • • • . • •••• • • • • •• • • • • • •• • ••• • • • •• s-c

0

in which ~a is ~ (A) (v)

The percentage change in the gas saturation deficit, (S-Ct)' for

any given unit of time is constant, based on the deficit at the be-

ginning of the time period, Equation 3. This relationship will plot

as a straight line on semi-logarithmic paper, (S-Ct) vs. t.

Equation 5 may also be rewritten as:

5.

log (s-c _) = -K_ t + log (s-c ) • •• • • . • •• •••••••••••• 6. e t -l,a e o

which may be considered to be a straight line equation of the form:

Y = mx + b, where Y = loge (s-et) and x = t. The slope (m) is -~a

and b is log es-c). e o

Appropriately plotted data of gas absorption vs. time should then

yield straight lines until saturation is nearly reached.

Page 21: Some effects of selected biodegradable detergents on the

IV • MATERIALS AND METHODS

A. Materials

The detergent samples studied were obtained through the courtesy

of Mr. Theodore Eo Brenner, Research Director, Soap and Detergent

Association, New York, N.Y. and Dr. James c. Kirk, Continental Oil

Company, Ponca City, Oklahoma.

14

Interim Reference Sample LAS Lot. No. 1-1 from the Soap and

Detergent Association was a blend of several unspecified commercial

linear alkylate sulfonates provided by several manufacturers and having

an analysis as follows~ (13)

linear alkylate sulfonate

sodium sulfate

free oil

water

molecular weight

60.8%

36.1%

0.4%

2.7%

348

"Nalkylene" 550 Alkylate Sodium Sulfonate -Sample No. 8302 D from

the Continental Oil Company has been commercially marketed since early

1965 (14). The detergent alkylate is derived from normal paraffins

of c10 , c11 , c12 , c13 and c14 hydrocarbons in such a ratio that the

molecular weight of the final linear alkylbenzene sulfonate prepared

therefrom is about 340. The normal paraffins are first chlorinated and

the resulting chloro-paraffins are used to alkylate benezene to make

the linear alkylbenzene. This product is then sulfonated with sulfur

trioxide and neutralized with sodium hydroxide to form a slurry (14).

The analysis of this sample was~

linear alkylbenzene sulfonate

unsulfonated alkylbenzene

46.5%

0.25%

Page 22: Some effects of selected biodegradable detergents on the

15

sodium sulfate 5.25%

water 48.0%

nAlfoln 1216 Alcohol Sodium Sulfate - Sample No. 8303 D also from

the Continental Oil Company was made from an alcohol blend of

approximately 65% dodecanol, 25% tetradecanol, and 10% hexadecanol which

was sulfonated with sulfur trioxide and neutralized with sodium

hydroxide to make a sodium alcohol sulfate slurry (14). The analysis

of the sample was:

alcohol sodium sulfate 30.1%

unsulfated alcohol 2.0%

sodium sulfate 1.1%

water 66.8%

Solutions of the three detergents were prepared with demineralized

water to give an active agent concentration of 1000 mg/1 of stock

solution. Detergent concentrations of 2, 5, and 10 mg/1 of aerated

liquid were chosen for use as this is within the range of reported

concentrations found in wastewaters.

The tap water for this study came from a well serving the

University of Missouri at Rolla. An analysis showed this water to have

a pH of 7.5, turbidity of 5 units and a total hardness of 220 mg/1 of

equivalent calcium carbonate of which calcium hardness comprised

115 mg/1.

The distilled water was obtained by condensing steam from the

school power plant. No analysis was made of this water.

Before being used, both waters were allowed to reach room tempera-

0 ture (23-24 C).

Page 23: Some effects of selected biodegradable detergents on the

16

B. Methods

Two liters of distilled water, tap water, or activated sludge,

including the detergent solution, were used as the experimental

aeration volume. The liquid, without detergent, was added to the

lucite aeration column, 4" I .D. X 27" high, (Figure 3) and the

dissolved oxygen, DO, was sparged with nitrogen gas. The nitrogen was

supplied from a compressed gas cylinder through a pressure regulator

and into the liquid through a diffuser. The DO content of the liquid

was reduced to approximately 0.2 mg/1 as the initial concentration

for each aeration period. The actual DO was determined with a galvanic

cell oxygen analyser (Precision Scientific Co., Chicago, Illinois).

The detergent was added following the sparging so as to avoid foaming

prior to commencing the aeration. Before starting aeration the liquid

was gently stirred to disperse the detergent.

After obtaining both the initial temperature and DO with the

analyser, the aeration was started at the rate of either 300 or 600

ml/min/1. These aeration rates correspond closely to those used by

Ludzack (15) for a laboratory model activated sludge unit. The air

flow rate was observed and regulated through the use of a rotameter

(Fischer and Porter Co., Hatboro, Pennsylvania).

DO and temperature readings were taken at one minute intervals.

The total period of aeration was governed by the time required for the

liquid to reach oxygen saturation as determined by the DO analyser.

The length of most periods of aeration was fifteen minutes, saturation

usually occurring within this time, however some check readings over a

period of thirty minutes to one hour were taken to assure no appreciable

change in DO had taken place after the initial series of readings had

been made.

Page 24: Some effects of selected biodegradable detergents on the

17

Figure 3. Experimental Equipment

Page 25: Some effects of selected biodegradable detergents on the

18

A check on each series of readings was made by repeating the test

with the same aeration rate after sparging the previously used liquid

(in the case of distilled water and tap water) with nitrogen. When

the liquid, rate of aeration, or detergent concentration was changed

the previously used liquid was wasted and the column thoroughly flushed

and rinsed before adding liquid again. A fresh volume of activated

sludge was used for each aeration period.

The activated sludge used in these tests was started from a "seed"

sanitary waste obtained from the outfall of the trickling filter

wastewater treatment plant south of Rolla, Missouri. It was grown on

a synthetic waste composed of the following constituents in the given

concentrations:

tap water ...•.....•...•..•.......•.............•. 100 ml/1

glucose ...........•.....•.•.....•................ 1000 mg/1

ammonium sulfate, (NH4) 2so4 .••••••••••••••••••••• 500 mg/1

ferric chloride, Fe(Cl) 3 .6H20 .••••••••••••••••••• 0.5 mg/1

calcium chloride, cacl2 .••••••••••••••••••••••••. 7.5 mg/1

manganese sulfate, ~so4 .H20..................... 10 mg/1

magnesium sulfate, ~;so4 .7H2 0 .••••••••••••••••••. 100 mg/1

1 M potassium phosphate buffer (pH7), K2HPo4 , KH2Po4 ••••••••••••••••••••••••. 10 ml/1

The following procedure was used for the once a day feeding of the

activated sludge units (Figure 4). The air supply was shut off and the

sludge allowed to settle for approximately thirty minutes after which

time the top 1.5 liters were siphoned off, the synthetic waste added,

and distilled water added to bring the volume to 3 liters. Aeration

was then resumed.

Page 26: Some effects of selected biodegradable detergents on the

19

The sludge used in the aeration tests had not been fed for 24 hours

and was in the endogenous respiration phase so as to minimize the effect

of its oxygen uptake. Eckenfelder and O'Connor (16) have reported the

endogenous respiration rate of activated sludge as 1.85 to 9.8 mg

02 1hrlg of sludge.

The biological solids concentration of the sludge was determined

by optical density using a Bausch and Lomb Spectronic 20 Colorimeter

(Bausch and Lomb Optical Co., Rochester, N.Y.) and a plot of optical

density vs. biological solids (Figure 5). The necessary dilution was

made to obtain a biological solids concentration of 1200 mgll which was

used in the tests. An optical density check on the solids concentration

was made following the dilution.

The dissolved oxygen, DO, content in mgll was determined through

the use of a galvanic cell oxygen analyser. The probe consisted of a

cylindrical silver cathode surrounded by a lead anode and set in a

ceramic material. The exposed end of the probe was covered with a pad

treated with potassium hydroxide electrolyte which in turn was covered

with a 1 mil thick polyethylene membrane held in place with a collar.

The probe was connected to a micro-ammete~JA a, calibrated to read

mgll DO. In order to determine the actual DO a probe sensitivity

coefficient, 0, was applied. Actual DO=}' a reading I 0. 0 was

determined for each test by calibrating the probe in a solution

identical to that used in the test. The Alsterberg (Azide)Modification

of the Winkler Method (17) was used to determine the actual DO content

of the calibration sample. 0 =~a reading I actual DO. The analyser

was also equipped with a thermistor for direct temperature reading.

For samples with temperatures different than those of the calibration

Page 27: Some effects of selected biodegradable detergents on the

20

rigure 4. Activated Sludge Units

Page 28: Some effects of selected biodegradable detergents on the

0.6

0.5

:r.. ~ 0.4 0 ..;:t U"\

.j...J

t1l

:>-. .j...J

•r-1 Cll s:: 0.3 <I)

A ..-1 t1l u

•r-1 .j...J

8' 0 . 2

0.1

0 100 200

Figure 5

Optical Density vs. Biological Solids

from

Dr. Don F. Kincannon Oklahoma State University

Stillwater, Oklahoma 1965

300 400 500 600

Biological Solids (mg/1)

700 BOO N f-'

Page 29: Some effects of selected biodegradable detergents on the

22

sample, ~ was adjusted by use of a scale provided by the manufacturer

of the analyser. During tests the probe was suspended at the approximate

mean depth of the liquid as shown in Figure 3 and manually agitated.

Page 30: Some effects of selected biodegradable detergents on the

V. PRESENI'ATION OF RESULTS

In order to present the effects of the selected detergents on

oxygen transfer, graphs were plotted of the dissolved oxygen deficit,

S - Ct, in mg/1 versus elapsed time, t, in minutes for each test

condition.

The value of the theoretical solubility concentration of oxygen,

S, was determined from Standard Methods (17). Ct, the oxygen

23

concentration in the liquid at time t, was determined from the corrected

oxygen analyser reading, tl a I ~.

The following Figures 6 through 23, showing the plots of (s- C ) t

versus t are arranged on the basis of liquid system (distilled water,

tap water, and activated sludge), aeration rate (300 and 600 ml/min/1),

and detergent studied (LAS #1, Alfol, and Nalkylene). Each figure shows

curves for the effects caused by 2, 5, and 10 mg/1 of a particular

detergent under the test conditions. A curve for the "blank", no

detergent in the aerated liquid, is also shown. References to the

effects of the detergents are made with respect to the "blank."

A. Distilled Water System

Theoretical oxygen saturation, (S-Ct = 0), was not attained in

this system at either aeration rate as evidenced by the fact that the

dissolved oxygen deficit curves became horizontal, indicating that

saturation had been reached, before Ct equaled S. From Figures 6 through

11 it may be seen that the theoretical oxygen saturation was more closely

attained by the 600 ml/min/1 aeration of the "blank" and the 300

ml/min/1 aeration of the distilled water containing a concentration of

2 mg/1 of LAS #1 than any of the other distilled water systems. To

varying degrees, all detergents may be seen to exhibit effects on R,

Page 31: Some effects of selected biodegradable detergents on the

the rate of approach to theoretical oxygen saturation, s, and the

dissolved oxygen deficit, s - ct.

24

From Figure 6 it may be seen that the 2 and 10 mg/1 concentrations

of LAS #1 increased R when aerating distilled water at a rate of 300

ml/min/1. The 5 mg/1 detergent concentration R was slightly less than

that of the "blank." The 5 mg/1 concentration increased the DO deficit

over that of the "blank" by approximately 0.02 mg/1 as apparent

saturation is reached, while the 10 and 2 mg/1 concentrations decreased

the DO deficit by approximately 0.1 to more than 0.3 mg/1 respectively.

From Figure 7 it may be seen that the 10 mg/1 concentration in­

creased R more significantly than the 2 and 5 mg/1 concentrations whose

initial R values closely corresponded to R of the "blank" when aerating

distilled water containing Alfol at a rate of 300 ml/min/1. All three

concentrations of Alfol produced a DO deficit less than that of the

"blank." At an Alfol concentration of 10 mg/1 the DO deficit at

apparent saturation was not significantly lower than that of the "blank",

however, the 2 and 5 mg/1 concentrations decreased the deficit by

approximately 0.14 and 0.16 mg/1 respectively.

From Figure 8 it may be seen that the R values increased slightly

with detergent concentration but did not differ greatly from R of the

nblank" when aerating distilled water containing Nalkylene at a rate

of 300 ml/min/1. All concentrations caused an increase in DO deficit

from that of the blank ranging from approximately 0.41 to 0.31 mg/1 for

2 and 10 mg/1 of Nalkylene respectively. The effects of the 5 and 10

mg/1 concentrations may be seen to be comparable to one another.

In Figure 9 (aeration rate of 600 ml/min/1 of distilled water

containing LAS #1) it may be seen that although the initial R values

increased slightly with an increase in detergent concentration they

Page 32: Some effects of selected biodegradable detergents on the

-~ :f

........ .. +)

0

I

Cl) .. ~ ()

•rl lH Q)

~

~ Q)

g '1:1 Q)

~ 0 11) .,

orl ~

25

8 •· 0 ~.lr-+---t--1--1---t--i--:+--t--t--r--r-.--.----r~ ~

6.0

5.0

4.0

3.0

2.0

1.0

0.8

0.6

0.5

0.4

- 'l\ - -- -- ---- - - --- t-- .. - . - -- -- ..

"' -- ~ ---

~ ~ r-- --l---f---1f----t--t--t---r--t - - - ---

~\ -- -- _\\. - --·

-== -~~~ -- ----t--t--1

-~~-+---~--~-r--~--t---r--- ---

·· t--- - __ ----::_ --1----1---- t----t-- '---

- --- -- f-- ---- -- . r---- ---- t--

-- t-- r--- --. Bl nk 0

-- - 2- ~gfl f-1!1 5 ~g/1 A

10 ~~ 1 --x

-- t--

1-------1---- - .. - -r--- --\\· - -~~ ~ - --

-~-- ---- ----- - ------ --- ~l ~~ -- --

- ---- ------ --- -~~~ l~~ -0.3 ~-_-+_ -__ -_ 4-_~~_-__ +-_-_+-~--~. ~~Jr~~-~:-1r------r~---~v~-----~r--- ~_ rr_-__ ~

f--- --- --- ---r---l--t---t-1~~ ..... ~ . --~ ---. ---- - - ----- ---+---0: -- - -r-----+==1~~~~---~

0.2 ~~--~-r--+--+--+--+--~~~;-~r-~~r--j-. ---- -- - -- -----r--\ -- -· :-·r-- - -

--r--- - - 1----- \ 1---

---t- ---t-- -- -r-- -~\ -

0.1~~--~--~_. __ ._~--~--~~--~----_. ________ __ 0 2

Figure 6.,.

4 6 8 10 14

Time, t, (mi.ri;)

D1ssq4ved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Di~tilled Water Containing LAS #1

,I',

Page 33: Some effects of selected biodegradable detergents on the

26

10.0

,....., r-l

' ~ ..._, .. +'

0

U) .. ...., ..,; 0

·ri 44 v

0

t:: Q)

bD

$ -o Q)

~ 0 II) II)

..,; 0

8.0 i :x 6.0

5.0

4.0

).0

2.0

1.0

\ ~ l~ -·-- --··- - ---- - - -- - - - -- -

- \\ ·-~- ··- r--- --1--- -· . - . ---

1--- ,~ ------ --- -

----- --- ~ \~ r-- - - ·-· - - -· -I--- 1--- - '---

~ - -- -· -- - ·-· I--'-

'\ \\ .. -. -- -· -· - - ·- f---·

- --· \ ~~ -- -- ,____ - '---·

\ '~ Bl nk 0 --· -- - - '1 gfl H1-

-\ ~ -· ·-- ---- ... - - -·

~ 5 pg/1 A -- ... -- -*·

~ r---

.LU ngt 1 ·-·- ·-

\ '\~

0.8 \ \ \ C\._ \'-.

0.6

0.5

0.4

O.J

0.2

\ f\ ~ - --f--- --I-'- 1-- -~ ~~ ~- --· ---- ·-- --

f-- -· -- -- --· -- --~'\ ~' ~ r---- !--- , ~~

~~ (\ ~ ~~ ' __ ,. -- ---- - -·--- - -·---- ~ 1--

l ' "'-.: " - · --- --- - ---- - -- - .. - 1--

- - ---- --- - - - N ~ -r--- - -· - --- - ~ ~ ----1

kc ........., ~ ~

-- - -· -·-- -- -· --- -- - _ _4 ~~

- ·--·

·- ··--f--- --·· "1

0.1 0 2 4 6 8 10 12 14

Time, t, (mill~ )

Figure~- Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Distilled Water Containing Alfol

Page 34: Some effects of selected biodegradable detergents on the

27

8.0 ~~~-t--!--+-t-r-+--+-+-1--+----t----+---l----l

\ 6.0 ---1[-·-5.0 \\.

f- -

4.or--r~\\~~4-_,--+--+--+-~--~~~~4--4--~~ - ~~k c---~-1---·1---1---- --f---·1---·- --

-f--- ------ --1----

-. --- 1---- --·

0.3 - --1---f.---

··- --·· ----- -- - --- --1---- -- --1---- -- ·-- --1---

-- f---- ·- -- ----- --1--+---- ---- ·- ---

0.2 ~-+--4---~-+--+-~--~--+--4--~--~-+--4-~~~ - -- . - -- -- --· --- -· --1-- -

- --- 1--- --!---·- - -+---1---- ----· ·- f--

--- --- -- --· - ---~~ -- --1---~-+- 1----+- - f-..

0.1 ~~--~~--~~--~~--~~--~~--~-L--~~ 0 2 4 6 8 10 14

Time, t, (llli;i~)

Figure~· Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Distilled Water Containing Nalkylene

Page 35: Some effects of selected biodegradable detergents on the

28

did not exceed the R value of the "blank", but corresponded closely to

it. The DO deficit increased with an increase in detergent concentration,

ranging from approximately 0.1 to 0.3 mg/1 for 2 and 10 mg/1 of LAS #1

respectively.

From Figure 10 (aeration rate 600 ml/min/1 of distilled water

containing Alfol) it may be seen that the R values for the 2 and 5 mg/1

concentrations were slightly less than R for the "blank'r, whereas, R

for the 10 mg/1 concentration was slightly greater than the "blank."

The presence of Alfol in all concentrations tested increased the DO

deficit over that of the "blankrr by approximately 0.3 mg/1.

In Figure 11 the Nalkylene displayed slightly increasing R values

with an increase in concentration when distilled water was aerated at

600 ml/min/1. The R values for the detergent concentrations, however,

were not greatly different from R of the "blank" in the early minutes

of aeration. The various concentrations of Nalkylene in this system

caused oxygen saturation to be reached at approximately the same time

and approximately the same DO saturation as one another. All Nalkylene

concentrations caused a DO deficit approximately 0.6 mg/1 greater than

that of the "blan~r at saturation.

B. Tap Water System

From Figures 12 through 17 it may be seen that for the test

conditions the oxygen saturation concentrations attained were less than

the theoretical oxygen saturation concentration by approximately 0.4

mg/1 or more. The rate of approach to saturation, R, for the aerated

tap water containing the tested detergents may be seen to vary from

values close to that of the "blankrr to values of R less than that of

the "blank."

Page 36: Some effects of selected biodegradable detergents on the

29

lo.or--r--r--r--r-,--r--,-~--~~--T-~--~~~

..........

~ ~ '-' ..

+) 0

I

Cl)

s.·o ~~-r~-r--r--t--+--+--l-+-+--+--t--+--l---J 1

6.0 \

5.0 ,

4.0

- ~ --- --

-- I---- ;-----

~\ - ~ - ----- - ------1---+--- 1---

,\ r---

3.0

2.0

~ - --- ------- ------ - - - -t---1-- 1----- - -

~rL --- -- :-- "' --- ----- --1--'--- ----~ ~\ - ·- - - --- -1--1----- -- ----- -·-- ---- - ------ ---

2 4 6

-- ---- -- - +--- --- ---- t--Blank <:>

. -- --- -- - -- £ " ifg/1.-a- --

8

5 ~g/1 A --- 1()~1~ --·-

1~ 12

Time, t, (mir1~)

Figure~. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Distilled Water Containing LAS #1

Page 37: Some effects of selected biodegradable detergents on the

30

1o.or--r--~~--~~--~--~-r--~~--~~--~--r-~

,......,

< ~ -.. ~

0

I

Cl) .. +l ....... 0

•rl 4-t d)

0

s:: Q)

bO g 't:1 Q)

> r-f 0 en en .....

Q

t

6.0 ' \

5.0 '

4.o L ~- . ~\ ----- --- - - -- --~----- ----

3.0

2.0

1.0

- ~\\ ---- ------ ----- -- - - ----- --· -- ---- - r----- '---w• -- -- -------- -- --~ --- -- -- ---- -- - ----

.. .. ~~---·--- ~~\ --

- ---Bl nk 0

-L ~g/1 ~-- ~--

5 rg/1 A --- f----- 10- ~g/1 )(

\\ \J~ 0.8

0.6

0.5

0.4

0.3 -- ~~ -=-~ = =-= :_-_- ~- --- --- -_-_ -~- ~~

-~=-~ ---_ ----- ----- --~ ------·--- '.. -- -- ---; 0.2 ~~-+--~~-4--+-~\+-~~--+--+~~,_-T~

---~- ---

-~- -~---~ -·-j~ -- --------·-

['., 0.1 -L-~--~~--~~--~~--~~~~~--~~--~~

0 2 4 6 •, 8 18 12 14

Time, t, (mill~)

Figure 10. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Distilled Water Containing Alfol

Page 38: Some effects of selected biodegradable detergents on the

; ,.

31

lo.or--r--r--r--~-r--r--r~--~~--~~--~~~

,...... .c! ~ ..._..

.. +)

0

I

Cl) .. +)

"" () ...... ~

C1) ~

s:: Q) bO g

't:1 C1)

~ 0 It) It)

"" Cl

8.·o .-ll-ll-t-t--+---+---1f---t--+--+-t--+--+-~

4.0

3.0

2.0

1.0

0.8

0.6

0.5

0.4

0.3

l -. -·

-- r---

.. - f--..- - -. - --f---- ---

··-·· ---·-· --r----- r- f--- -- :------·

Blank (!) --z mg/1 -a

5 mg/1 &. -- 10~, -x-

--------

·------ - --1\ -- - ·-\'~- - --- .. -- ---- ----. ----- . -- ----. f-

-

--- -- ---- - "' -~- ~-~- --~~ ~~:~_-=::____ - r---\---- ----- ---·- ---- -- ------- --

0.2 r--+--+--_~-.~. -- ~--~-~ __ ~\ __ +_--+-_-.. _~ .. _-___ ~------~---~~-----+--+~

- ---- -·-. -· -~ - -- - -- -- -

.. - - - - - - -. -- ·--- ----~ --1-----lf-- f-- --- -

' 0.1 ~~--._~--~--~~--~~--~~--~--~_. __ ._~ 0 2 4 6 8

Time, t, (miri~)

G> 10 12 14

!igure It. Dissolved Oxygen Deficit ·vs. Time for 600ml/min/1 Aeration of Distilled Water Containing Nalkylene

''· .. . . .' ~:·~~ ~, .. /~,~·*·,;"'·

Page 39: Some effects of selected biodegradable detergents on the

From Figure 12 it may be seen that the R values were decreased by

the presence of LAS #1 when aerating the tap water at a rate of 300

ml/min/1. At the end of 10 minutes aeration, as oxygen saturation was

approached for the systems containing the LAS #1, the 2 and 5 mg/1

detergent concentrations may be noted to have caused a DO deficit of

approximately 0.17 mg/1 greater than that existing for the "blank".

The 10 mg/1 concentration exhibited a DO deficit of approximately 0.12

mg/1 greater than the rrblank" after the same period of aeration.

From Figure 13 it may be noted that all of the concentrations of

Alfol caused a slower approach to oxygen saturation, lower R,than that

shown by the "blank" when tap water was aerated at 300 ml/min/1. It

may be seen that the 2 and 5 mg/1 concentrations of Alfol caused a DO

deficit at 12 minutes which was greater than that in the "blank" by

32

0.12 and 0.02 mg/1 respectively but were still approaching the deficit

shown by the "blank." The 10 mg/1 concentration approached oxygen

saturation with a deficit less than that of the "blank" by approximately

0.1 mg/1 after 14 minutes of aeration.

From Figure 14 it may be seen that the R values did not vary greatly

for the 300 ml/min/1 aeration of tap water containing Nalkylene. The

10 mg/1 concentration of Nalkylene reached oxygen saturation with

approximately the same deficit as the "blank." The 2 and 5 mg/1

concentrations may be seen to have DO deficits less than that of the

"blank" by approximately 0 .OS and 0.12 mg/1 respectively after 13

minutes of aeration.

In Figure 15 (600 ml/min/1 aeration rate of tap water containing

LAS #1) it may be seen that the R values for the systems containing

the LAS 411 were slightly less than that of the "blank", but no

significant difference in R appeared among the detergent concentrations

Page 40: Some effects of selected biodegradable detergents on the

33

1o.or--r~--~~--r--r-,--~~--~~~--~~~

a.·o 1\i\--t-r---t----t--t-~--:+--f--+-+-+-+--+--t.-l H\rt-~r-r4-+~~~+-~~-L~

6.0 ,, 'K

5.0 ~\\~~+--+-___ +_- __ t---+--1---+--+--~-l--L.J_J \\ --- r-- f--

4.0 ~ >----- -(~- _, __ ----- - -------

~ 3.0 ~~ -~ - \' -· - - -- --·- - -- ;---- ---- - -s -~~-~- -=---.... ~ ~

0.3

----- --- -- --Bl~nk 0

..... -L~f-8 ---5 lng/1 A

- 10 ngy-i -x- ... -

· - ·-- -i---- --- f--

--- ---- ------- ----· -- --- --- --- -- --- --- --1-- - -- ---- - 1- --+--1-- ·

--- ----- ----- -----+---~- -- -------1

----~-

-·-- -----· -· ·----- ----- - - --t--·1---1--1--~-

' --- ---- ---- - - --- - - f---f--f---- ....._-+--+--1

0.1 -L-~--~~--~~--~~~~--L-~--~~--~~~

0 2 4 6 8 10 14

Time, t, (miri~)

Figure 42. Dissolved Oxygen Deficit vs. Time for 300 ml/rnin/1 Aeration of Tap Water Containing LAS #1

Page 41: Some effects of selected biodegradable detergents on the

34

1o.or-~r~--~-r~--~-r~--~~~~--r-~~~

8.0 ~\~--t-t--t--f--+~~~+-+--+---t---t-L--1

~ 6. 0 --\\:- '---- ---- -··- - -- f--- --

5.0 \'~ ---- --------\ J..'\ - ----·

4.0 \~\

~~~

------------

0.3 ---- --l----1----- -

--- -----1------------1--- !---- -- ---· ----r---

-- ·--· -···· - --- -- . - . ---- --- ----- -- >-- ---· -··· ·-

0.2 r--+--+-~~-r--+-~--~--~-+--4---~~--+-~--~ --- f-f-- -

-------------- ----1---t--f-- --- --1--

·- ... -- --··· ----- ·---- -----1---+-·-

0.1 L-~--~--._~--~--~~--~--._~--~--~~~~~

0 2 4 6 8 10 14

Time, t, (~l)

Figure ~3. Dissolved ,Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Tap Water Containing Alfol

Page 42: Some effects of selected biodegradable detergents on the

10.0 ·r-..,---,-.,--r-r--r---,-..,..--,..-.,..--,----,-..,...---.--..

8 •· 0 1\\-t-t--t--t--t-11-+--+--+---t-+--1---+---!.--J

\ -- f--- ----- --6.0 -- ~ ~ -- --- ---- ---

5.0 " ----------e---- --- --- - --1----4.0 ,, l

,&- '--··· · \\\ , - ,---- ---t---1--- 1----1-- i-- --1---

---- - 1-1--1--- --1-- ------ ---1--- --·1----1---~-- --1-- ----- ---1---

--- -----· -----1-- --- 1-

---- 1--- -- -- - -- -- - - --· -- --· ---- -- 1---- 1--- - --- -

---- --- --1-- +--1--1-----1--- t--•----+---1--t--r--

-----f--- - - - --

0.1 ~~--~_. __ ._~--~~--~~--~~~~--~~~

0 2 4 6 8 10 14

Time, t, (miri~)

Figure tb. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of 'fap Water Containing Nalkylene

Page 43: Some effects of selected biodegradable detergents on the

36

themselves. As the DO saturation is reached, all the concentrations

may be seen to have a DO deficit of approximately 0.3 mg/1 greater than

that of the "blank .n

From Figure 16 (600 ml/min/1 aeration rate of tap water containing

Alfol) it may be seen that increasing the concentration of Alfol caused

an increase in R, but only the 10 mg/1 concentration increased R to a

value greater than that of the "blank." No significant change in DO

deficit at saturation may be noted from that of the "blank."

In Figure 17 it may be seen that all of the concentrations of

Nalkylene caused decreases in R over that of the "blank" when aerated

at a rate of 600 ml/min/1. The greatest differences in the DO deficit

from that of the "blankrr at saturation, 0.28 and 0.20 mg/1, were

exhibited by the 5 and 10 mg/1 concentrations respectively. Saturation

was reached after nearly the same aeration period in all instances.

C. Activated Sludge System

From Figures 18 through 23 for the activated sludge system it may

be seen that the rate of approach, R, to oxygen saturation of the liquid

and the DO deficit, S - C , were affected to varying degrees by the t

type and concentration of detergent present. The rate of aeration may

also be seen to have an effect. By increasing the aeration rate from

300 to 600 ml/min/1 the increase in rate of oxygen transfer in the

rrblanks" was approximately doubled in the early minutes of aeration.

The DO deficit at saturation in the "blanks" decreased with the in-

creased aeration rate from approximately 3.6 mg/1 at 300 ml/min/1

aeration to 3.35 mg/1 at an aeration rate of 600 ml/min/1. It may be

noted that this system at saturation was the furthest from theoretical

saturation of the three liquid systems studied.

Page 44: Some effects of selected biodegradable detergents on the

37

1o.or--r-,--~~~r-,--.--~~~--~--~-----

-.c:! ~ ......., .. ~ I

Cl) .. +) ...t ()

...t f+-4 Q)

~

s:: Q) bO g '0 Q)

~ 0 11) 11)

...t Q

8.·o l\~1---t-t--t--t--+-+-+-+---t----.j~!-..L-L_J

\ 6. 0 '--\t-r-r-r __ = t-_-__ i-t-__ -_ t_-__ l--1-·~~- -1--1--+--4--_ -J_ -___ _j

5.0 J

4.0

3.0

2.0

1.0

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0.6

0.5

0.4

.... [ "' --t---1--- ·1---f--- --

" ---r-~~~~.---+-~1- ---1---r---t--t---t--~-+-+-- t--·

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- -- ·- t---t---+-- --1-- lf-- f- - 1---BUank E)

\ 1----l--- --r--~ ~ -- · - - -- 1-- -··- ·- f-1--

--------- -----. ---· _ _c~b 1--- -- f--­r--

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A )( --- - -

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---· --- -- - -- -- - -- --t--·t---1 ---1--

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-- --------1--- -1-1-- ---- ---~

--- 1--- ---~ ---1--r---- ·- 1--

0.2 r--+--~-+--+--+--+--4--4-~--4-~~~~--~~ ----·- -· ____ .. -1-----1-- ·+---1----·-·-

---- ·-- --1--+-- --1--1---J.--+--~-- -- --I-

-·-· --·--- -- ----- --+--- -----t---t--,~-+-~-+--+-~

0.1 ~~--~~--~~--~~--~~~~~~--~~~ 0 2

Figure );..5.

4 6 8 10 12 14

Time, t, (mifi;.)

Dissolved Oxygen n'eficit vs. 'l'ime for 600ml/min/1 Aeration of Tap Water Containing LAS #1

Page 45: Some effects of selected biodegradable detergents on the

,..... .c! rf .._, .. 0~

(/) .. ~ ..... () ....

f+..4 Q)

0

s::: (1)

i '0 Q)

~ 0 Cl) Cl) .....

0

4.0

3.0

2.0

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0.8

0.6

0.5

0.4

0.3

·- -- ----+---- -- ·--

·- - --t--J--J.--1--r--t--+---1--

1\\ --t--\\-\oh\\c-- 1 --- --

38

·_ . ~~l\c ---_ -= ~--- -- 1-f--1--K\\ ~ -1--· -- f-- --. f----

---1---1-- --f--- "\.\ --1-- -- t-- ---· !---- ·-·~ . ""'K + --- 1--·-·

-- --- --t--1--- - 1----

-- 1--1--- 1--+--~ 1--- -

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0.2 r--+--r--+--+--+--+--4--4-~--~--~~~~~~ ---- -·-- -- ---- - 1-- ---1----1---1-1---t---~-

- 1---- - 1---t---1---f--1---+--.J--1---1---~-il--

-·- -- - --- ---1- -1--

0.1 ~~~~--~--~--~~~~---L--~--~~~~--~--~~ 0 2 4 6 8 10 14

Time, t, (Ddil)

Figure 16. Dissolved Oxygen rieficit ·vs. Time for 600 ml/min/1 Aeration oJ Tap Water Containing Alfol

Page 46: Some effects of selected biodegradable detergents on the

,-...

~ ~ ........ .. .+)

u I

Cl) .. .+) ..-1 ()

..-1 ....... Q)

0

t:: Q) tiO g

"d

~ 0 It) It)

..-1 0

39

10.0

a.o l 1\ 6.0

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\ -\ - ---- 1----- --- ---·· - - ·· f.----- -- - -

~

4.0

3.0

2.0

1.0

~ -- 1---1--- --1--- - -- - -· -- . --

~\ 1--1--

~\ -- -- - -- -

-- ----~· ~ -- -- --· - - .. - 1---f-- 1--f.--- -- ·- - --- -·- -- --1-- f-·-1--· --- 1---

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----I~ l ---· -.\

- ·-· tlnk ·- --Bl G)

t--2-~ ·"'1 1:\

\ ~\ --- -- - · -·- - --

~~1 · t--

5:1. • ·-~-- ----

~~ ~ - - ---· - iU-' ,!uX ~/J

- -

\~ "' """ O.B \ ~ "' ....... ~

\\ ~ ~ f-..-~

0.6

0.5

.. ~ ~ .......... ~·~

1--- - 1--- ----~ ~- ----- 1---- --- - -- . ·-·-· ··- - -

1--I--1-- -- - ~~ N L lr· 1-- 1---~

0.4 '

-·-- -- ---- -· --- ----·· 1--1-- -

0.3 --· - ·--· -- ---- ---- -· ·-- f-- -- f.- - -· ----- -- --f--- 1----f---

-- ---- ---·-- ·- --- ---- ---- -- -· t---

0.2 - --· -· --· --- ----1- - -· -

---· --1- -- -

·- --- - t---

0.1 0 2 4 6 B 10 12 14

Time, t, (JDiil)

Figure l7. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Tap Water Containing Nalkylene

Page 47: Some effects of selected biodegradable detergents on the

40

From Figure 18 (300 ml/min/1 aeration of activated sludge con­

taining LAS #1) it may be seen that an increase in the concentration of

LAS #1 increased the DO deficit at saturation by approximately 0.2 to

0.4 mg/1 for 2 to 10 mg/1 of LAS #1 respectively.

The effects of increasing the aeration rate to 600 ml/min/1 are

shown in Figure 19. The 5 mg/1 concentration of LAS #1 may be seen to

have increased the DO deficit slightly. The 2 and 10 mg/1 concentrations

decreased the DO deficit by approximately 0.3 and 0.15 mg/1 respectively.

The presence of Alfol in concentrations up to at least 10 mg/1 in

the activated sludge under aeration at the rate of 300 ml/min/1 did not

significantly affect the DO deficit at oxygen saturation compared to the

"blank" as may be seen from Figure 20. Concentrations of 5 and 10 mg/1

increased the rate of approach, R, to oxygen saturation over that of the

"blank."

From Figure 21 it may be seen that while the increase in aeration

rate from 300 ml/min/1 to 600 ml/min/1 caused a decrease in DO deficit

at saturation for the "blank" of approximately 0.25 mg/1 it increased

the DO deficit for the activated sludge containing Alfol. This increase

was greatest for the 2 and 5 mg/1 concentrations, having raised them by

approximately 0.4 mg/1 over what they were at the 300 ml/min/1 aeration

rate. The 10 mg/1 concentration caused no change in effect from that of

the "blan~' at the aeration rate of 600 ml/min/1.

From Figure 22 it may be seen that the 10 mg/1 concentration of

Nalkylene initially increased the R value over that of the "blank" a t

300 ml/min/1 aeration. The other concentrations had R values closely

corresponding to that of the "blank." All studied concentrations of

Nalkylene reduced the DO deficit at this rate of aeration by

approximately 0.2 mg/1.

Page 48: Some effects of selected biodegradable detergents on the

41

From Figure 23 it may be seen that for the increased aeration

rate (600 ml/min/1) all initial R values for the Nalkylene concentrations

in the activated sludge corresponded closely to that of the "blank." The

DO deficit as compared to the "blank" increased by approximately 0.1 mg/1

for the 2 mg/1 concentration, remained unchanged for the 5 mg/1

concentration and decreased by 0.3 mg/1 for the 10 mg/1 concentration.

Page 49: Some effects of selected biodegradable detergents on the

42.

1o.or-~r~--r-~~~--r-~~~--r-,-~--~~~~

,......,

<!. ~ ......., .. rf I

Cl)

8~o r~"~-t---t-r-t-+--+-+++-+-+-t--J_J

6.0 ~~~~~- .. -- --t--t--t-t-_-t_ ._-___ -+-+-+----l--+--!---1 5.0r-1!-1~_,~~- ~~t~~t--r~--+--+--~~~--+-~_j 4.0

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~ 1.0 r--t--t-~r--t--t-~--~--~-+--4-~~~--~-t~ Q)

Cl ~ 0.8 r-1-r--t-t--t--t--t-+---f-+~--1---1-+-~

» o.6r-~~--r-~-+--~~-+--~4--+--~~-+~ "0 ------ -- --- --- --- - -- -- --- -- --- ---··· -- ---i 0.5 ~~--1r~~-t_-_--t---r-~---_ -_+_--~t-~~---4----~~----~---_4--_-_+~-----~~ ~ 0.4 r--T--~~r-~--+--1--~--~-+--4---~~--+--+--~ iS

J ... ' ·:. - !

--1---- - -- --- 1-- -

0.3 ---- - -- f-- --

. -- --- . --- ---1--- - - . -- ----

. - - ---1---+- ------ --

-- 1-- -- --- --1---+--

0.1 ~~~~--~--~--~~~~--~--~--~~~~--~--~~ 0 2 4 6 8 10 12 14

Time, t, (mii~)

Figure l8. Dissolved Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of ~tivated Sludge Containing LAS #1

Page 50: Some effects of selected biodegradable detergents on the

4:3

10.0~~--~~--~~--,-~--~~~~~~--~~~~

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0

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Cl)

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--~- -·----- -·-- -- --- 1----f--t---1-- ----f-------------- ----· ·-- ---

~ 1.0 r--;---+---r---r--1---~--r-~~-4---+--~--+---+-~~-; (1)

Q

s::: Q) bD g

1---t-- --1- - -- ·--- -· --- ·-- c-- --- --· - ._

- --1-- --· 1--- -----·- --- r---- ,.-

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0.3 ---1---t--+----- ---

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-·-- -- -- ----. - -+--

O.lL-~--L-~--L-~--~~--~~~~~~--~~~

0 2

Figure 19 . ...

4 6 8 10

Time, t, (miJil)

Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Activated Sludge Containing LAS # 1

.._ · ' ,· •.

Page 51: Some effects of selected biodegradable detergents on the

-) -.. +)

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Cl) .. +) of"!

3.0

2.0

44

- --- ·---f--- ---

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0

s:: Q)

g --- -- --- ~- ---- ~-+--- --- --- --- ----- -· 1---l--'t1

Q) ~ 0.5 ~-t--+-~--4-~~~--~-+--+--+--~~--~--~~ 0 ~- -- 1-- --- -- ----- - ·- -- --- 1-·- --- 1--· ---'--l-It) It) 0.4 r-~r--t--~--~--~~---+--~--+---~-4--~--~--~~ E ------ f-·-- ----~--~---~---~--~-

0.3 r-~--r--r--r-~--~~~--4--4--~~--~~~ ·· - -- - ---r-- t---·-- -- - ,_____ --

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0.2 r--+--r--+--+--+--+--+--4--4--4-~--~~--~~ ----- ----f----- - - ,------- ~

- · -- -- ---t---l--1----4--t---t--+--4--

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0.1 ~_. __ ._~--~~--~~--~~--~~~~~~~~

0 2

Figure 2_0.

4 6 8 10 14 " .·:.

Time, t, (miri~) Dissolved Oxygen Defi~it vs. Time for 300 ml/min/1

Aeratibn of A~tivated Sludge Containing Alfol

Page 52: Some effects of selected biodegradable detergents on the

........ -c! If -.. +)

0

(/)

... · ..

45

---- f----- ---

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------· -- ---+---~------- 1--- -- ----. --1--1--

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--- f----- --+--+--~-+--t---+----1

0.1 ·~~--~~~--~~--~~--~~--~~~--~~

. ·.:

0 2 4 6 8 10 12 14

Time, t, (mi.Ji~)

Figure ~1. Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of ~tivated Sludge Containing Alfol

:: ' .... /:~·~·:'~· .. ,·; .. .

Page 53: Some effects of selected biodegradable detergents on the

46

-- f-----

., -- .. -- -- ----· . -- -·- ·-- - 1--t-- t - -t--t--lf--1---J--'-

- - ,.---- 1---- -- -- ---

3.0 --c! ~

------ ------- - -- - ---~---r---r--~--4----~--+------

-- --- ---t---1--- 2.0 .. +)

u -------:----1---Bl ink C!>

--- - ----- ---I

Cl}

----1---+------- --- --· --- - -- - 2 '- 'l!gif~I:--•-- c-----

---- _. __ __ ---_.!!.P811 A >-.AN, Dg}' l, 'IK: ..

~ (.)

~ 1. 0 r----t--t--t--t-+-+--+-+-~--J--+--+-~--+--1 Q)

0

r:: Q) bO g

---~--- 1-- ---- -

-----· -- 1- ------1-- - -- - -

0.3 ' -- - -1---1-- -- ----- f- -

----1----- ----- --- - - 1----------

-- -1---- --- ---- - ----- ------ ------ ----1---

0.2 r--+--~~~-+--+--4--~--~-+--4---~~--+--+--~ --- . ---1----t--+----- --~--1-- -- --

---- --~--1--- -----1-----f--1---

------ --------- - - ---1---+-- 1---+--t---1

0.1 ~~--~~--~~~~--~~--~~--~--~~--~~ 0 2

Figure 22 • ...

4 6 8 10 12 14

Time, t, (~~) Dissoived Oxygen Deficit vs. Time for 300 ml/min/1 Aeration of Aet~vated Sludge Containing Nalkylene

Page 54: Some effects of selected biodegradable detergents on the

47

1o.or-~r~--~-r~--~-r--r-,--.--r-~~--r-~

a.·o ~~~~~-r-t--t--t--+--+-t-l-+-+--+---l---J \

6.0 ~ ----------

5.0 '~---t- lf-.J--

4.or-~~~~*~~r-,_-+--~~-4--+-~~--+-~~ "'~

- -- f--- ----

--f--- -

3.0 - ----r------- ----·- -· -----t---t--+--4--~-1..__--

~ llf

--1---... --1---'--1-- ---- ----1---<1---1--- - f----- - - - f---

..._, 2.0 ..

+) u ------f---- -- - --- --- ---J---1--+--

t--1--1·------ -- ----· ---

. __ . _____ ----.. +) ..-I ()

~ 1.0 r--1---t--~--t---r-~---t--4---+-~~-+--~--+---~~ Q)

Q

~ Q) bO g

---·- --1--..-- 11--- 1·- -f---- - - f-·-- --- - 1-- -· f--- -'t1 Q) ~ 0.5 ~-T--;---r--+--~--r--+--~--+--+--~--~-+--~~ 0 1-- ---1- ----· -· --·-- --f- -- - f-- -· II)

., 0.4 tS 1----1·-~--l------- --- f--

0.3 r--+--+--+--+--+--+-~--4--4--4-~--4-~--~~ -·. --- ·-- -- f-- -- --

-- --1- f--- -- -- --- -- - --~ ·--· ---- -- --1------

----- --- ---- -- ---- ------ -- f-- --f---- --

0.2 r--+--+--4~~--+-~--~--~-+--4---~~--+--+~ -1----1---- --- --'---· -- ---- ---

-- - - -- t---1----t-- 1--1---lr---~--4--- --- -- f-·-f--

Q.l ~~--~--~--~--~~--~--~--~--~~--~--~--~~ 0 2

Figur~ 23 . ....

4 6 8 10 12 14

Time, t, (mill~) Dissolved Oxygen Deficit vs. Time for 600 ml/min/1 Aeration of Act~vated Sludge Containing Nalkylene

Page 55: Some effects of selected biodegradable detergents on the

48

VI. DISCUSSION OF RESULTS

A. Distilled Water System.

Comparison of Figures 6 through 11 shows that the higher rate of

aeration (600 ml/min/1) caused a more rapid approach to saturation than

did the lower rate of aeration (300/ml/min/1). The DO deficit, (s -C), t

of the "blank" at saturation decreased from approximately 0.33 mg/1 for

the lower rate of aeration to less than 0.1 mg/1 for the higher rate of

aeration.

The higher rate of aeration produced the following effects in

distilled water with the presence of detergents as compared to the

effects of the detergents in distilled water at the lower rate of

aeration. The 2 and 10 mg/1 concentrations of LAS #1 showed an in-

crease in DO deficit of approximately 0.1 mg/1 while the 5 mg/1

concentration showed a decrease of slightly less than 0.1 mg/1. The

10 mg/1 concentration of Alfo1 showed no significant change in DO

deficit for the increase in aeration rate, however, the 2 and 5 mg/1

concentrations showed increases of approximately 0.13 and 0.22 mg/1

respectively. The 2 mg/1 concentration of Nalky1ene decreased the DO

deficit by approximately 0.1 mg/1 at the 600 ml/min/1 aeration rate

as compared to the DO deficit for the same detergent concentration at

oxygen saturation for the 300 ml/min/1 aeration rate. The 5 mg/1

concentration of Nalkylene increased the DO deficit by approximately

0.03 mg/1. The 10 mg/1 concentration of Na1kylene caused no change in

DO deficit at apparent oxygen saturation.

In decreasing order of their overall effect in decreasing the DO

deficit over that of the "blank" in distilled water the detergents are

Nalkylene, Alfol, and LAS #1.

Page 56: Some effects of selected biodegradable detergents on the

49

B. Tap Water System

It may be noted that the rate of approach to oxygen saturation, R,

did not differ greatly for similar aeration rates between the tap

water and distilled water systems with no detergent present. It may be

seen, however, that the "blanks" for the two systems reached saturation

with different DO deficits for the same rate of aeration. The "blank"

for the tap water showed an increase in DO deficit over that of the

distilled water amounting to 0.17 mg/1 and over 0.4 mg/1 for the 300

and 600 ml/min/1 aeration rates respectively.

Increasing the aeration rate from 300 to 600 ml/min/1 in the tap

water caused a more rapid approach to saturation. The increased rate

of aeration decreased the DO deficit of the "blank" from 0.5 mg/1 to

nearly 0.4 mg/1. The increased rate of aeration did not significantly

affect the DO deficits for the tap water containing the varying

concentrations of LAS #1 except as compared with the DO deficit of the

nblankrr for the same aeration rate. For the 600 ml/min/1 aeration ratE.

the difference in DO deficit at saturation between the "blank" and

detergent concentrations was approximately 0.1 mg/1 greater than it was

at 300 ml/min/1 aeration rate. The Alfol exhibited more consistency in

effects for varying detergent concentrations in the tap water at the

higher aeration rate. The 5 mg/1 concentration of Nalkylene exhibited

a notable effect on increasing the DO deficit at saturation from

approximately 0.35 mg/1 at 300 ml/min/1 aeration rate to 0.69 ml/min/1

at the 600 ml/min/1 rate of aeration.

In descending order of their effect on increasing the DO deficit

in tap water the detergents are LAS #1, Nalkylene, and Alfol.

Page 57: Some effects of selected biodegradable detergents on the

C. Activated Sludge System

From Figures 18 through 23 it may be seen that all detergent

concentrations and "blanks" increased their rate of approach to

saturation when the aeration rate was increased.

50

The decrease in DO deficit for the "blank" which occurred with the

increased aeration rate in the activated sludge was comparable to that

which occurred for the distilled water (approximately 0.25 mg/1)

although the total DO deficits are not comparable. The decrease in DO

deficit for the increase in aeration rate for the tap water was less

(approximately 0.1 mg/1).

By comparing Figures 18 and 19 it may be seen that all

concentrations of LAS 4F1 caused a DO deficit in excess of the "blank"

at an aeration rate of 300 ml/min/1, whereas, at 600 ml/min/1 aeration

the 2 and 10 mg/1 concentrations of LAS #1 caused a DO deficit at

saturation less than that existing for the "blank."

From a comparison of Figures 20 and 21 it may be seen that in­

creasing the aeration rate caused an increase in DO deficit of

approximately 0.5 mg/1 over that of the "blank" at saturation for the

2 and 5 mg/1 concentrations of Alfol while the curve for the 10 mg/1

concentration of Alfol nearly coincided with that of the "blank."

It may be seen by comparing Figures 22 and 23 that the comparative

changes in DO deficit were affected primarily by the change in deficit

for the "blank" at the different aeration rate. Except for the actual

decrease in DO deficit as measured from theoretical saturation for the

10 mg/1 concentration of Nalkylene the actual deficits of the 2 and 5

mg/1 concentrations remained nearly unchanged.

Of the three detergents studied the Nalkylene caused the least

detrimental effect on the oxygen transfer in the activated sludge.

Page 58: Some effects of selected biodegradable detergents on the

D. Overall Oxygen Transfer Coefficient, ~a

In order to better understand the effects of the individual

detergents and their concentrations on the overall oxygen transfer

coefficient the values of ~a were determined in the following manner.

From the derivation of Equation 4,

-d dt s-et

= K la dt

the limits of C are reversed which eliminates the negative sign

preceding the integral.

or

log e

or

~a =

c 0

-d dt s-c

t

(s-c ) (s -c~) =

=~a

~a

(s-c ) 0

log e (s-et)

t

d t .••••••••••••••••••••

t

.....................

51

7 •

8.

S-C is the initial dissolved oxygen deficit when time, t, equals zero. 0

S-C is the DO deficit at time t. t

From the plots of DO deficit versus time, Figures 6 through 23, the

values of ~a were calculated for the initial straight-line portion of

the curves.

For example: Figure 7. ~a for 2 mg/1 of Alfol in distilled water

at an aeration rate of 300 ml/min/1.

~a=

log e

t

S-G0 \

S-C -~ =

log e

(8.38) (0.89) = 6

-1 0.374 min

Page 59: Some effects of selected biodegradable detergents on the

The values of ~a were then plotted versus the detergent

concentration for each detergent in each liquid under the two rates of

aeration; Figures 24, 25, and 26.

From Figure 24 it may be seen that in the distilled water system

all three detergents caused a varying degree of decrease in ~a at the

lower concentrations. ~a for the 10 mg/1 concentration exceeded that

of the aerated distilled water without detergent for all detergents at

both rates of aeration •. The increase in rate of aeration from 300 to

600 ml/min/1 may be seen to have caused approximately a SO percent

increase in ~a·

From Figure 25 it may be seen that the initial ~a values for the

tap water system were approximately 0.05 units greater than they were

for the distilled water. As with the distilled water the lower

concentrations of detergent caused a decrease in ~a which then in-

creased for the 10 mg/1 concentrations of detergent. With the

exception of the ~a value for the Alfol at 600 ml/min/1 aeration, the

increases were not sufficient to raise the ~a values to those of the

blanks for the corresponding rate of aeration.

52

From Figure 26 it may be seen that no significant decrease in ~a

occurred from the presence of detergents in the activated sludge system

when aerated at 300 ml/min/1. A slight increase in ~a values may be

observed for all detergents as their concentrations increased during

this aeration rate. At an aeration rate of 600 ml/min/1 the presence

of LAS #1 and Alfol may be noted to have caused an initial decrease in

~a values over that of the rrblank", however, 10 mg/1 of Alfol caused

an increase in ~a· All concentrations of Nalkylene had ~a values

greater than that of the "blank"at the higher rate of aeration.

Page 60: Some effects of selected biodegradable detergents on the

....... o.6 7

LAS #1 e e Alto1 ..__ _ _. Na.l.ky1ene >E--- -- -K

Aeration Rate a 600 ml/min/1

~ _0. 5 __ __....

.. ------~ --~ 0.4 .... ;:;;-:....,:;:;_;;::;~:::;:=:~:::;:::~---=-=i- - - - - -----1 -- ..:::= --t----=- -

Aeration Rate • 300 ml/min/1

o.o ~--~----._ __ _. ____ ~ __ _. ____ ~--~--~~--~--~ 0 1 2 3 4 5 6 7 8 9 10

Detergent Concentration, (mg/1)

Figure 24. KLa vs. Detergent Concentration in Distilled Water

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0.3

0.2

0.1

LAS #1 E> G) Alfo1 4--- - --A Nal.ky1ene X- - - --~

Aeration Rate a 6oo ml/min/1 __ ____. ---­__..---- ---------

--------- -----"..__ ___ .,____ _____ .. Aeration Rate • 300 ml/min/1

o . o ~--~--~~--~--~----._ __ _. ____ ~--~--_.--~ 0 1 2 3 4 5 6 7 8 9

Figure 25.

Detergent Concentration, (mg/1)

K vs. Detergent Concentration in Tap Water La

10

54

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55

LAS #1 0 0 Altol .t. -~ Nal.ky'lene ~---- -K

Aeration Rate • 60o ml/min/1

------~--------~-------------~ --0.3

0. 1 Aeration Rate • 300 ml/min/1

0.0 ~------~--~----~--~--_.--~ ____ ._ __ ~---J 0 1 2 3 4 5 6 7 8 9 10

Detergent Concentration, (mg/1)

Figure 26. KL.Ys. Detergent Concentration in Activated Sludge

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VII. CONCLUSIONS

The manner and extent of the effects of each detergent on the

three liquids under the two aeration rates studied have been discussed

in the preceding section. From this study the following conclusions

have been reached:

1. The detergents studied varied in the degree to which they

affected the dissolved oxygen deficit as compared to a

similarly aerated sample having no detergent content.

In descending order of their adversity to the DO deficit

for each system the detergents rank as follows:

a. Distilled Water - Nalkylene, Alfol, and LAS #1

b. Tap Water -LAS #1, Nalkylene, and Alfol

c. Activated Sludge -LAS #1, Alfol and Nalkylene

2. An unqualified statement as to the effect on ~a should

not be made for these detergents. For example, in Figure

24 it may be seen that ~a may be less than or greater than

that of the "blankn for different concentrations of the same

detergent. The degree to which ~a differs from that of the

"blank" may be affected by the rate of aeration. (Note the

Alfol in tap water, Figure 25)

3. The lower concentrations of detergent caused a decrease in

K_ which then increased for the 10 mg/1 concentration. -La

Eckenfelder and Barnhart (10) have reported similar effects

for sodium lauryl sulfate, NaLS04 , at a concentration of

25 mg/1.

4. An attempt at estimating the effects of detergents on ~a in

56

activated sludge based on ~a values for similar concentrations

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of detergent and similar rates of aeration in distilled water

or tap water may lead to erroneous conclusions. For example

the increase in ~a over that of the "blank" caused by all

concentrations of Nalkylene in the activated sludge as com­

pared to its effects in distilled water and tap water.

5. Based on the observed effects of these selected "soft"

detergents, a change in present aerobic wastewater treatment

is not necessary to satisfy the respiration requirements of

the microorganisms. This is evidenced by the fact that a

minimal dissolved oxygen concentration of 0.5 to 2.0 mg/1 is

usually required and over 4.0 mg/1 existed at equilibrium

in the activated sludge system.

6. While the increase of approximately 0.5 mg/1 in DO deficit

at saturation which occurs in two instances with the

activated sludge may not be critical in the treatment plant,

such a decrease in DO could be critical in a receiving body

of water already having a minimal DO content capable of

supporting fish life.

57

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VIII • RECOMMENDATIONS FOR FUTURE STUDY

The following recommendations are made for consideration for

further studies.

1. The use of a magnetic stirring device or mechanical agitation

might be used to achieve the necessary velocity past the face

of the oxygen analyser probe. A recorder for the analyser

might also be considered.

2. Additional samples might be studied with particular emphasis

on their effects in the waste treatment processes and the

bodies of water which receive the effluents containing the

~d~.tddelt;ergfj!,llts .,, .

3. As a variation1 a shock loading of detergent might be applied

to see what effect the detergent has on a system already

saturated with oxygen.

58

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59

BIBLIOGRAPHY

1. SAWYER, c. N. (1958) The effect of synthetic detergents on sewage treatment processes. Sew. and Ind. Wastes 30, p. 768-774.

2. McKINNEY, R. E. (1962) Microbiology for sanitary engineers. McGraw-Hill, New York, p. 223.

3. MANCY, K. H. and OKUN, D. A. (1965) The effects of surface active agents on aeration. Jour. Water Poll. Cont. Fed. 37, p. 212-227.

4. HOLROYD, A. and PAKRER, H. B. (1952) Investigations on the dynamics of aeration - the effects of some surface contaminants. Jour. and Proc., Inst. Sew. Purif. 4, p. 280.

5. MANCY, K. H. and OKUN, D. A. (1960) Effects of surface active agents on bubble aeration. Jour. Water Poll. Cont. Fed. 32, p. 351.

6. LYNCH, W. 0. and SAWYER, c. N. (1954) Physical behavior of synthetic detergents. I. Preliminary studies on frothing and oxygen transfer. Sew. and Ind. Wastes 26, p. 1196-1200.

7. LYNCH, W. 0. and SAWYER, c. N. (1960) Effects of detergents on oxygen transfer in bubble aeration. Jour. Water Poll. Cont. Fed. 32, p. 25-40.

8. MANGANELLI, R. (1952) Detergents and sewage treatment. Sew. and Ind. Wastes 24, p. 1065-1068.

9. ZIEMINSKI, s. A., GOODWIN, c. c. and HILL, R. L. (1960) The effect of some organic substances on oxygen transfer in bubble aeration. Tappi 43, p. 1029-1032,

10. ECKENFELDER, W. W. and BARNHART, E. L. (1961) The effect of organic substances on the transfer of oxygen from air bubbles in water. Amer. Inst. Chern. Engr. Jour. 7 ' p • 6 3 3 - 6 34 .

11.

12.

HANEY, P. D. (1954) Theoretical principles of aeration. Jour. Amer. Water Works Assn. 46, p. 353-376.

LEWIS, w. K. and WHITMAN, W. G. (1924) Principles of gas absorption. Ind. Engr. Chern. 16, p. 1215.~1220.

13 BRENNER T E (1966) Personal communication. . ' . . 14 KIRK J C (1966) Personal communication. . ' . .

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15. LUDZACK, F. J. (1960) Laboratory model activated sludge unit. Jour. Water Poll. Cont. Fed. 6, p. 605.

16. ECKENFELDER, W. W., Jr. and O'CONNOR, D. J. (1961) Biological waste treatment. Permagon Press, New York, p. 42.

60

17. STANDARD METHODS FOR THE EXAMINATION OF WATER AND WASTEWATER (1960) 11th Ed., Amer . Pub. Health Assn., New York, p. 309-312.

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61

VITA

Donald Ernest Modesitt was born at Richmond, Indiana on October

14, 1936 to Mr. C. Keith Modesitt and Mrs. Lorene May Modesitt. He

received his primary education at schools in Indiana, Michigan,

Illinois and Missouri. He graduated from Hannibal High School,

Hannibal, Missouri in May 1954. He graduated from the Missouri School

of Mines and Metallurgy (now the University of Missouri at Rolla) with

a Bachelor of Science Degree in Civil Engineering in May, 1958.

Mr. Modesitt has experience as a civil engineer with the highway

departments of Missouri and Illinois, and the National Park Service.

He was course supervisor of the Rod and Tape School, at Fort Leonard

Wood, Missouri while on active duty with the U. S, Army. Since

September, 1960 he has been an Instructor in Civil Engineering at the

University of Missouri at Rolla.

He is a registered professional engineer in the State of Missouri;

a member of the Missouri Society of Professional Engineers, American

Society of Civil Engineers, American Water Works Association, Missouri

Water Pollution Control Association, Chi Epsilon Civil Engineering

Fraternity, and Delta Sigma Phi Social Fraternity.

On October 10, 1959, Mr. Modesitt was married to Miss Linda L.

Rogers. They are the parents of three sons, Brian Dale, Keith

Bradley, and Paul David.