19

SURFACTANTS & DETERGENTS

Effect of LAB composition on LAS performance

inear alkylbenzene sulfonate (LAS) continues 10 be the most widely used surfactant in the world. Currently. on a global basis. more than four billion pounds of linear alkylbenzene (LAB). the feedstock used 10 make LAS. are consumed annually. In addition. several new plants are under construction in the world today. The popularity of LAS is simple to explain: LAS has an exceptional costperformance profile. and has proven human safety and environmental acceptability. However. there is some uncenainty related to LAS in terms of understanding how variations in strucrure impact performance. There are two reasons for this confusion: (a) formulations have become more concentrated. which effectively magnifies differences in the formulatability among commercial products. and (b) new technologies have been developed to manufacture LAB which have a greater variation in composition. The purpose of this article is to clarify how commercial LABs can vary in composition. and how these variations affect the performance of

This article was prepared for by Michad F. Cox and Dewey L. Smith, Condea Vista Co.. 12024 Visla Parke Dr.. Austin. TX 78726.
INFORM

........

position of the benzene ring along the paraffin chain, and concentration of a coproduct called dialkyltetralin. These variations in composition remain

Figure 1. Linear alkylbenzene (one po .. lble Isomer ot dodecylbenzene)

LAS.
Introduction The LAB molecule consists of a linear paraffin chain attached to a benzene ring (Figure I). Commercial LAB. however. consists of a blend of LAB molecules that vary in terms of paraffin chainlength,

intact when LAB is sulfonated to form the finished surfactant, LAS. The most important factor in terms of LAB composition is average molecular weight. Increasing the average molecular weight increases surface activity and solution viscosity, but decreases water solubility and water hardness tolerance. The inverse is true when average motecu-

tar weight is decreased. Optimal average molecular weight depends largely on use conditions (such as temperature, water hardness, and concentration). The second-most important factor in relating LAB composition to LAS performance is the concentration of dialkyltetralin (OAT). OAT sulfonates readily and completely to form dialkyltetralin sulfonate (OATS). OATS aCIS as a surfactant. a hydrcrrope, and a viscosity modifier. Consequently, high OAT-containing LAB (with 6-10% OAT) is preferred for LAS intended for liquid formulations because less (or no) additional hydrotrope is required to achieve desired solubility and viscosity. Because OATS is nearly as surfaceactive as LAS itself, the presence of OAT in LAB has little effect on LAS performance. The distribution of phenyl isomers contained within a commercial LAB

Chlorina1ion Paraffin Chlomparaffin +

benzene

Aiel} catalyst

LAB (high 2-phenyllhigh dialkyhelralin)

LAB (low 2-phenylllow diaJkyhetraJin) HFcalalyst Dehydrogenalion Paraffin I Olefin (-,""',...,,...,.,.. Solid alkylation catalysl LAB (high 2-phenylllow dialkylteuaJin) LAB (high 2-phenylllow dialkyltetralin)

benzene

Figure 2. Commereial

processes tOl" LAB production

INFORM. Vol. 8. no. I (January 199n

20

SURFACTANTS & DETERGENTS

"'~~----;::::=:===;-]
CII-Avg. LAS

C1rAvg. LAS
... C13-Avg. LAS

Table 1 Solubility (cloud polntl') 01 LAS as a function of average carbon chalnlength (15% of LAS with 1% sodIum sulfate)

Cloud point Cu-Avg. LAS CtrAvg. LAS Cu-Avg. LAS

-0 Coocenlnltion of LAS [Jog C (gIL)] (increases from lefllo right)
" Teml"'",.ure hi&hn"..-.e which KJ!ubili.y) IO'I> ~Iu';""$

("C) 2.5 20.5

63.4
01" LAS .urn
~
\(I.

ckludy (. \ovI'er cloud poin empenlun:

Figure 3. Surface tension (at 2S"C, with 0.01 M N~O.,to buffer ionic strength).I. functlon of concentration for C,,-average LAS, C1z-lIVI!ntge LAS, and C13-e YeflIge LAS

8000 700l
6000

"5000

l
"

'"

4000

300l 200l 100l 0

II

12
Average LAS carbon chainlenglh

Il

Figure 4. The effect 01 molecular weight on viscosity

5

(25% LAS, 30C, shear rete ..

e-1)

also can influence solubility and viscosity, because it affects the way LAS molecules pack together in solution. A higher concentration of the 2- and 3phenyl isomers generally improves LAS solubility. Although the effect of phenyl isomer distribution is smaller in magnitude compared to the effect of OATS, it can be significant. particularly when LAS concentration is high. or in the presence of high ionic strength. Although understanding the relationship between LAB composition and LAS performance is important in obtaining maximum cost-effectiveness. such understanding also is difficult because several variables are involved. and the effect of these variables depends on the conditions under which the LAS is being used.
INFORM, Vol. 8, no. 1 (January 199n

Why variations occur Manufacture of LAB is accomplished by connecting a paraffin chain 10 a benzene molecule. Chemically, this is achieved through the Friedel-Crafts alkylation of benzene with chloropar affins or olefins and an alkylation catalyst. Although many possible catalysts could be used, only three are used commercially: aluminum chloride (AlCI). hydrofluoric acid (HF), and a newly patented solid alkylation catalyst (patent number U.S. 5196574). Commercial routes used to manufacture LAB are illustrated in Figure 2. Commercial LAB can vary in terms of average molecular weight. DAT content, and phenyl isomer distribution.

Average molecular weight Commercial LAB is produced from the alkylation of benzene with various blends of Cw c., CI2, Cn. and CI4 linear chloroparaffins or olefins. Different average molecular weight LABs are available. normally averaging in the 232 (CII) to 260 (Cn) molecular weight range. This specific molecular weight range provides both acceptable solubility and surface activity. Increasing molecular weight above 260 produces a LAS with better surface activity but very low water solubility. Decreasing molecular weight below 232 produces a very soluble LAS which has poor surface activity. The effect of LAB molecular weight on surface activity and water solubility is shown in Figure 3 and Table I. LAS molecular weight also has a significant influence on LAS solution viscosity, as shown in Figure 4. This is why high molecular weight LAS slurries usually have high viscosities, and are more difficult to handle in comparison to low molecular weight LAS slurries. Optimal LAS molecular weight is determined by the conditions under which the LAS will be used. LAS reacts with water hardness ions (calcium and magnesium) to form insoluble salts. This interaction can effectively remove LAS from the wash liquor. lowering its concentration and effectiveness. Lower molecular weight LAS is much less sensitive to water hardness than higher molecular weight LAS. and is therefore normally used in formulations that do not

.------------------------------------------------------------21

contain ingredients which control water hardness (builders). This is why CII LAS is typically used in unbuilt laundry liquids and dish washing liq-

uids.
The effect of LAS molecular weight on detergency performance is illustrated in Figure 5. As shown. optimal detergency performance under low water hardness (50 ppm) conditions is obtained with a higher molecular weight LAS. while a shorter carbon chain length is best under high water hardness conditions. Overall performance decreases with increasing water hardness because water hardness ions interact with soils and solution components in addition 10

'" , ,
s
'a

-a 1l ~

75 I70

Permanem press

~ !!.

"" il
"

- - ...

--.
14

" 60 , I! &

g 55 I9
l:I~

,
10
1\ 12

~ ~ SO

_e-. 50 ppm water hardness.... - 150 ppm water hardness --b- 300 ppm water hardness 13

I'

LAS.
The effect of LAS molecular weight on foam stability (dishwashing performance) is shown in Figure 6. Again. optimal performance is obtained with a high molecular weight LAS under low water hardness ccndinons. and with a low molecular weight LAS under high water hardness conditions. Note that. contrary to what is observed in detergency. overall foam performance increases with increasing water hardness because water hardness ions help stabilize LAS at the air-water interface (help strengthen the foam). This is why manufacturers sometimes add mugnesium salts to dishwashing liquid formulations. Another factor related to molecular weight which can affect performance is carbon chain distribution. Carbon chain distribution (the relative distribution of CI(). CII' C12 C13 and CI4 homologs) affects LAS performance properties by determining average molecular weight. but it also can affect performance if it changes the relative concentration of the lesser performing (or better performing) homologs. For example. C\O LAS and CI4 LAS are good surfactants. but CI4 LAS is not very soluble. and CIO LAS is not very surface active. If the carbon chain distribution were "peaked" so that average molecular weight remained the same but the ccncencations of C\O LAS and Cl4 LAS were significantly reduced. then pertermance would be enhanced because the concentration of the better performing

LAS carbon chaintength

75,-------------------,
~

1
'a

"

~------

70

j
!!.

65

..
t-

..-------.-------~------~ - _ .. ... ..
---Conoo

160
~
K.

I5OL9

g 55
L10

_ LII

50 ppm water hardness-I50ppmwotcrhardnc:ss

Jt

~L-_-I>- ~JL_pp_m __ w__"1'_h._ro_.,. __ __l

12 13 14 15

LAS carbon chainlcngth

Agure S. Detergency performance 01 LAS homologa, ea meaaured by Vllta Lab Method 30391 (high 2phenyl/hlgh OATS-type LAS at SO, 150, and 300 ppm water hardneaa; 16% LASI3O% sodium trtpo/ypholphate (STPP)llo% 11Iieate formutatlon; 0.15% concentratlon, l00"F, .. bumfduataoltl

homologs (CII CU, and Cn) would be increased. In practice, varying the distribution of homologs requires more specialized paraffin feeds, which naturally would increase manufacturing costs. However. variations do occur and should be taken into account when selecting an LAB. In summary. LAB (or LAS) molecular weight is by far the most impor-

tant factor to consider when formulating with LAS. Other variations in composition play significant but secondary roles. OAT level Alkylation normally results in a single attachment between the paraffin chain and a benzene molecule. Sometimes, however. attachment can occur twice to form OAT or dialkylindane. The tNfORM. Vol. 8. no. 1 (January 199n

22 SURFACTANTS & DETERGENTS

-0-.0 ppm water hardness __ - 50 ppm water hardness

-/:r-

150 ppm water hardness

zs ]

Table 2 Phenyl isomer distribution for "hIgh 2phenyl" and "low 2-phenyl" ell average LAB Phenyl Isomer High 2
phenyl

e 20

, ,.,,

, -,
, .,0 ,,

Low 2phen)"

~ ~ 0
0.

/ /

,
~"

distribution

distribution 18

~
E
0 0

rs

10 ~ e
-e

"
~-----.<>'

", ,

2-Phenyl
3-Phenyl 4-Pheny\

, , , , , ,
b
13 14

J2 20
17

5-Phenyl 6-Phenyl 7-Pheny\

20 " 24
18 I

"

"

10

"us

12 carbon chainlcngth

"

Figure 6. Foam ltabillty (dllhwalhlng performance) of LAS homolog' (formulatIon .. 24% LASi6% lauryl3-mole ether lutfalei'l% laury1 myristyl mono-elhanolamlde; at 0, 50, and 150 ppm walar hardnallj. Plales soiled with vegetable shortening; hand dlshwashIng lasl performed with 0.05% formulations USing Vista Lab Method 31192.

o
Dialkyhndnnc (one of many possible isomers) Dialkyhetralin (one of many possible isomers) Figure 1. TWo possible coproduct structures

es
60

...

C12 LAS COATS

E ss
~

:s

~ 50

-e .~

40

~ , ~ as
30

zs

-3

_2.5

_1.5 LogC (gIL)

-I

-'1.5

Figure 8. Surface tension venus

log (C) of C12 OATS and e12 LAS

structure of these coproducts is shown in Figure 7. Levels of OAT and dialkylindane are detennined primarily by the alkylarion process itself. The chloroparaffin/Aiel] process produces alkylate that contains 6-8% OAT, while the olefin/HF. olefin/AleI3 and olefin/solid alkylation catalyst processes produce alkylate generally having less than 1% OAT. Levels of indane in all processes are low. generally below the ability to measure them. OAT readily sulfonates to form OATS. A misconception is that OATS does not contribute to performance. OATS, however, is nearly as surfaceactive as LAS itself (Figure 8). The only difference between LAB and OAT is a second attachment between the alkyl chain and the benzene molecule. This second attachment makes the molecule more rigid. which enhances its ability to affect solubility and viscosity without significantly reducing its surface activity. OATS acts as a "structure breaker." which improves water solubility and lowers viscosity (Figures 9. 10). This is why chioroparaffin/AlCI3 LAS is preferred for liquid formulations: it is easier to formulate, and less expensive in terms of hydrotrope COSI. because of the presence of OATS. Although OATS has a significam impact on solubility and viscosity. its presence does nOI have a significant effect on performance because it is surface active (Figures 11 and 12).

INFORM. Vol. 8. no. 1 (Jonuary 1997)

23

Table 3 low 2-phenyl distribution of CIIand Cu' average LAB

5Or;:=:::::::;::=-=:::::;---~ _A-. High 2phcnyllhigh

DATSCI1 LAS ...... _ High 2phenyl/low OATS CI1 LAS ....... Low 2phcnylllow OATS CI1 LAS

Phenyl isomer

CII"
everage

CU' a,-erage

2-Phenyl 3-Phenyl 4-Phenyl S-Phenyl 6-Phenyl 7.Phenyl

18
I.

I.

20 2'
18
I

" " 23 "

22 _10 10

--

---"

~~

~.~
20
('lo.

Phenyl isomer distribution During the alkylation process, the benzene molecule can end up attached 10 any carbon along the alkyl chain (with the exception of the terminal methyl groups), Two possible isomers are illustrated in Figure 13. The "phenyl isomer distribution" refers to the relative concentration of LAB molecules in which the benzene group is attached to the second carbon of the alkyl chain. the third carbon of the alkyl chain. the fourth carbon. and so forth. The phenyl isomer distribution obtained during alkylation is dependent almost solely on the alkylation catalyst. Alel3 and the proprietary solid alkylation catalyst give what is normally called a "high 2 phenyl" distribution, while HF gives a "low 2-phenyl" distribution, The "2phenyl" designation is used simply to distinguish between the two major types of alkylute (Table 2). Phenyl isomer distribution is affected by carbon chain distribution or average molecular weight. A higher molecular weight means that the average chain length of the alkyl chain is longer, which means that more isomers are available. For example, a CII LAB molecule has five possible isomers (2-phenyl, 3-phenyl, a-phenyl, 5phenyl, and 6-phenyl), while a Co LAB molecule has six possible isomers (2-phenyl. j-phenyl. a-phenyl. 5phenyl. e-phenyt. and 't-pbenyl). Increasing the molecular weight therefore results in a broader distribution since more isomers are possible. This is illustrated in Table 3.

. __ ---'L_---' __ ---' __ --'-__ --'--_---l

LAS concentration
..... .-,.

-pc.-......,.....,_ ........... - ...... ..,.)

.,-..,...--. wIodIlOto _"'LAS (a_

Figure

9. LASaolubillty:Ioud point) II. function of (:onc:enlnltion(2%

salt Iddecf)

7~h===~;=~==~----------~
_A-. High 2.phenyllhigh
OATS CI1 LAS ......_ High 2-phenyl/low DATSCII LAS ....... Low 2phcnyl/low DATSC11 LAS

6000

/ /

3000 -

~L,-------W~------~3L,-------l~c-------.L,C------150
LAS coocentllnion Figure 10. VlSCOltty venul ('lo) shear

percenllge LAS(30"C.

rate",

10 sec-1)

Phenyl isomer distribution has little effect on performance (Figures I I, 12) except with respect to water solubility and formulatability in liquid products.

Under practical use concentrations. when LAS is dissolved in water, most of the LAS aggregates into micelles. and the remainder stays in solution as individual molecules called
INFORM. VOl. 6. no. 1 (Jonuory 1997)

24

SURFACTANTS

& DETERGENTS
J
4

Table 4 CompoSition 0' commercial LAB

,
6

2 J

Property
Average carbon chain Percentage 2-phenyJ Percentage dialkyllctrni inlindane

AICIJ-calalyzed alkylation C11-C1)

HF-catalyzed alkylation CII-C13

Solid-calalyxed alkylation
2-Phenyt isomer

CI:,-CJ3

27-30

15-24

21-30

6-10"

<I

<I
5Phenyl isomer

Q<I\1, irolcfi"' .... uJQi ;~ad 01ch~1IJ.

Figure 13. Two po .. lble phenyl isomers

LAS carbon chainlength Flgur. II. Detergency performance 01 LAS homolog., .1 measured by Vllta Lab Method 303-91 [high 2-phenyllhlgh OATS-type LAS VI. low 2'phanyll1ow OATS-type LAS II ISO ppm wlt.r hardn ... ; 16% LASI3O% STPPflO% eiueete formulation; 0.15% concentration, lOO"F, .. bum/dult 80U)

as

-,...

High 2-phenyl/high

DATS LAS

; 20

monomers. As the solution is cooled. the monomers precipitate individually as their solubility limit is reached. The temperature at which each monomer precipitates depends on its inherent solubility and concentration. The monomer concentration. in turn. depends on the composition of the micelle. It is possible to calculate the composition of the micelle and from this. the concentration of each monomer. From each monomer concentration and its inherent solubility. it is possible to predict the temperature at which the solubility will be exceeded. Experimentally. it is found that a high 2phcnyl LAS distribution has a higher solubility than a low 2-phenyl LAS distribution. This is why high 2phenyl LAS is preferred for liquid formulations. The bottom line It is important to understand how LAB composition can vary. and how these variations can affect performance. The composition of commercial alkylates is given in Table 4. The impact of compositional variables is somewhat dependent on the application. In general, molecular weight is the major factor since it controls both surface activity and solubility. A high OATS content and/or a high 2-phenyl isomer distribution makes it easier and less costly to formulate a liquid product.

~ -a ~ 0 ~
E
0

~10
e
-e

" ,,
10 12 IJ

"

14

LAS carbon chainlcnslh

"

Rgur.,2. Foam Itllbility (dlahw hlng perlor~nc:.l of LAS I'Iomologl, a. measured by Vista LIb Method 311-92.. (formulation" 24% LASJ6'l1oLauryl3-mo1e ether lulf.tel2% 'auryl myrIlty1 mono-elnanolamlne; high 2-phenyllhigh DATs-type LAS, and low 2-phenylllow DATS-type LAS)

INFORM. VOl. 8. no. 1 (Jonuory 1997)

28 SURFACTANTS

8. DETERGENTS

Current environmental issues for surfactants

The most complete and desirable process for determining the environmental acceptability of commercially used surfactants is commonly referred to as risk assessment. In this process. field monitoring studies are done to determine concentrations of a surfactant in environmental compartments of interest. such as wastewater treatment plant effluents, surface waters, sediments. or soils. It also is possible to estimme environmental concentrations by applying models which predict the fate of chemicals in the environment. The measured or predicted field concentrations then are compared with the concentrations of the surfactant known to be toxic to organisms Jiving in the affected environmental compartrncnrs. If the measured concentrations are less than the toxic levels, a margin of safety exists, and the surfactant is considered to be environmentally acceptable at current use levels. Even though this approach is the most desirable process for determining the environmental acceptability of surfucumts. it is expensive in terms of time, manpower. and money. At times, evaluations have been made without utilizing the whole risk assessment process, thus resulting in misconceptions and erroneous conclusions that persist in the marketplace. These are: (a) claims that oleochemical-based surfactants are environmentally preferable to petrochemical-based surIactants: (b) claims thai surfactants which don't manifest anaerobic biodegradation in certain tests wil1 accumulate and harm the environment: and (c) undue reliance on laboratory biodegradation screening test results for estimating the environmental fute of surfactants.

TIre fol/owing article was written by AII~n M. Ni~/srn of Condra Visfa Co., 12024 Vista PaTh! Dr.. AlISlin, TX 78726.

Environmental acceptability of surIactants

Over the last several years. claims have been made that oleochemicalbased surfactants are environmentally preferable to petrochemical-based surfactnnts. For example, papers making such claims were given at the 3rd CESIO International Surfactants Congress in London, United KingINFORM. Vol. 8. no. 1 (January 1997)

dom. in 1992. and at the 3rd World Conference on Detergents in Montreux. Switzerland. in 1993 (1-3). These claims are based, in part, upon results from laboratory biodegradarien test results in which differences in biodegradation rates have been observed. Because of the significant business and political implications of such claims. two major studies to evaluate these claims were undertaken by the European surfactant industry (4.5) and the Dutch government (6). The first approach taken was to examine the environmental impact of producing surfactants by doing a Life Cycle Inventory (LCI). An Lei consists of determining the amount of energy and raw materials consumed 10 produce a surfactant and its feedstocks as well as quantitating the amounts of atmospheric, waterborne, and solid waste emissions intrinsic to these processes. This study was very thorough in that all of the commercially important oleochemical- or petrochemicalbased surfuctunts were analyzed (4.5). A summary of this massive study is shown in Table I. which depicts an overview of the total resource requirements and environmental releases involved only in production of these surfactants (data are from Tables 2, 3, and 4 of Reference 5). An evaluation of the requirements and releases occurring during torrnutauon into detergent products was not included in this study. The surfactanrs are listed in the left-hand margin. with a notation of whether they are derived from petrochemicals (Pc). oleochemicals (Oc). or a combination of both. The

information presented includes requirements for raw materials. consumption of energy. and atmospheric. waterborne. and solid waste releases. All data are normalized to the production of 1000 kilograms of the surfncrant. These results show no clear differences in the overall amounts of energy and raw materials consumed or emissions produced between the oleochemical- or petrochemical-based surfactants. Since there is no agreement within the scientific community as to how to rate the environmental impact of the emissions and consumptions, no impact assessment was done. However, the overall conclusion from the study is that the potential impact from producing either oleochcmicalor petrochemical-based surfactants appears to be about the same. This conclusion is clearly stated in the abstract of the summary paper for this study (5): "Based on the findings. no unequivocal technical rationale exists for claiming overall environmental superiority. neither for production of individual surfactants nor for the various options for sourcing from petrochemical and oleochemicaVagricultural feedstocks and minerals. The value of the study lies in allowing each manufacturer to assess opportunities for improving the environmental profile of its surfactants and intermediates." The second approach, mandated by the Dutch government (6) and supported by the surfactant industry. particularly the Dutch Soap Association (NVZ). consisted of an exhaustive risk assessment for the four

29

Table 1 Overview of total resource requirements Surfactant"

and environmental

releases geteeses

Requirements Raw materials (kg/JOoo kg) Energy consumption (GJflOOO kg) Atmospheric (kgllOOO kg)

Waterborne (kg/JOoo kg)

Solid waste (kg/lOoo kg)

LAS AS

p,

1040 1091
2077 1310 2167 2167

61
73 57 73

1661 2604 1684 2335 2024 4451

1261

5 7 26

65 81
75

oe
p,

Pc

AE,

oe Sao. oe
SAS AE,

67 50
52

2.
.5 2 6 28 6 21 11 35

68
96

144
64

Pc

1013 1448 2401 1570

2264

oe, Pc
Pc

Pc

83 73 7. 72 82 63
p"tro-

2366 2044 2281 2062

2299 2015
and olt:ochcnlicak

67 66
64 64

AE,
AEII

Oc,Pe Oc,Pe

2064 2060

63
142

APG

oe

a Pc. pelnxhrmical;

Oc *oleochcmi<:al; 0.:, Pc = derived from borh

major surfuctnnts used in The Netherlands: linear alkylbenzcnc sulfonate (LAS). alcohol cthoxylates (AE), alcohol ether sulfates (AES), and soap. This study. which took over five years to complete, consisted of four phases: (a) collection and evaluarion of published and unpublished data from laboratory and field tests for environmental fate and effects of these surfactants, (b) estimation of environrnentul concentrations by the use of accepted modeling techniques, (c) actual field monitoring of LAS, AE, AES, and soap in wastewater treatment plant effluents and downwaters in The stream receiving Netherlands, and (d) calculation of safety margins between surfactant levels in the environment and their effects on the organisms living there. Dutch government officials concluded that these four surfactants (based on oleochemicals and on petrochemicals) were acceptable at current use levels. and further analysis was not required. In the official letter to the chairman of the Dutch Parliament dated

30, 1995, Minister of Public Housing, Physical Planning. and Environmental Management (VROM) Margaretha de Boer wrote: "A very extensive inventory was made by the detergent industry of the available ecoroxicologtcat data of these four ingredients. These data were subscquently evaluated by RIVM (National Institute of Public Health and Environmental Protection), after which, in consultation with industry. the Maximum Tolerable Risk level (MTR) for surface waters was determined. The

o.

MTR values for the four ingredients (listed in Table 2) turn out 10 be in the same order of magnitude for LAS. AE, and AES. The MTR of soup appears to be clearly lower. This can be explained by the absence of chronic toxicological data for this substance. However, the tentnnvc results of a chronic study with soap indicate that the toxicity of soap is comparable to that of LAS, AE, and AES. This means that the MTR of soap is presumably higher than listed in the table.

Table 2 Maximum tolerable risk (MTR) level and negligIble risk levels (VR) for surface waters of four detergent Ingredients
Ingredjente LAS AE AES MTK (]Jg/L)b VR (]Jg/L)b

250 110
400 27

2.5
1.1

Sao,

4.0 2.7

" Valucs ..,

b VaIuo:s

forCu ~s. CuEOu "E, (),,,EOu AES. fordi ... ",h-..1 .......... in .....race "'"Mer$.

INfORM. Vol. 8. no. 1 (Jonuory 1997)

30

SURFACTANTS & DETERGENTS

Table 3 Removal of LAS from a German (Edewechterdamnl Deposition 1986 period Age (years) 0.5

sludge-only

landfill

1983-1985 1979-1983 1975-1979 1972-1975

1-3
3-7 7-11 11-14

LAS concentration (mglkg) 9160 8610 3170 1560

245

"For the research to the actual exposure in the aquatic environment. in a cooperation between NVZ. RLZA (National Institute of Surface Water and Wastewater Management). RIVM, and the University of Amsterdam. a monitoring study was performed on the concentrations of the four ingredients in influents and effluents of seven sewage treatment plants. Subsequently, modeling was used to make an estimate of the concentrations of the substances in surface waters. From this monitoring study, it becomes clear that the removal of the substances in sewage treatment plants is almost complete (99.1-99.8%). As a consequence, the expected concentrations in the surface waters (PEC) close to the plants are low, about a factor of 100 below MTR level. Therefore, it can be concluded from this risk assessment that the environmental risks for the use of these substances in (luundry and cleaning) L&C products are acceptable by disposal to normal-functioning sewage treatment plants. Assuming that this is the case in The Netherlands, I appraise the usage of these substances as acceptable in every respect." All of the ecotoxlcologtcat data were normalized to LAS: C11.6: AE: C\J.3 EO:S.2 AE5: Ct2.S E03.4 since these are representative of the commercial surfactants present in the aquatic environment in The Netherlands (6). Other evaluations done by the European Union for laundry detergent ecolabel (7) and the British government (8) confirm the general conclusion thai currently used surfactarus including those derived either from petrochemicals or oleochermcals are not a threat to the environment at curINFORM, VOl.8, no. 1{January t99n

rent use levels. The above studies demonstrate the value of utilizing all the 1001s available instead of relying solely on laboratory biodegradation tests to arrive at imponant conclusions concerning the environmental acceptability of surfacrants.

Significance of 'anaerobic' biodegradability There has been concern that surfactants will accumulate and persist if biodegradation is limited in anaerobic environments. This concern has resulted in requirements for anaerobic biodegradability in certain ecolabel programs in Europe and Scandinavia (7,9). These are the result of an incomplete evaluation of existing data as well as the fact that no overall risk assessment evaluation has been done for chemicals in anaerobic environments. Strictly anaerobic environments are much less prevalent in nature than aerobic or microaerophilic environments, and they typically house a minor portion of the total volume of surfacmms released to the environment. Anaerobic habitats also playa transitory role in the biodegradation of surfactants since these reach the environment as components of domestic and municipal wastewater and are extensively exposed to aerobic conditions before. during, and after wastewater treatment
(10).

The anaerobic biodegradation test method most commonly required in the ecolabel programs is found in the European Chemical Industry Ecology and Toxicology Centre's (ECETOC's) Technical Report No. 28 (11). This method consists of placing the surfactant in a sealed bot-

tie with a nutrient medium and sewage sludge and then measuring the gaseous products of anaerobic biodegradation with time. This method only simulates the environment found in anaerobic digestors used in wastewater treatment plants in which sludge from the process is exposed to anaerobic digestion in a closed tank. The ECETOC method does not simulate what is happening in other so-called anaerobic environments such as landfills. sediments, and flooded soils. In these actual environmental compartments. exposure to oxygen occurs often by various mechanisms such as diffusion of gaseous oxygen. exposure to water with dissolved oxygen. physical disruption by air or water movements, and action of the biological populalion. More evidence that exposure to oxygen is occurring in these compartments is that aerobic and facultative anaerobic as well as strictly anaerobic bacteria can be cultured from these environments (12). The fate of LAS in so-called anaerobic environments illustrates the erroneous conclusions which can be formed if one only considers the results from laboratory anaerobic biodegradation tests such as the ECETOC No. 28 test method. The initial step in biodegradation of LAS requires oxygen (13) so LAS fails the ECETOC No. 28 lest; however, there are examples which demonstrate that LAS is nOI accumulating in "anaerobic" environments such as sediments or landfills. Table 3 is a summary of LAS analysis done in a German sludge-only landfill. This landfill is from 8-10 meters deep and has been in operation since 1972. It receives digested sludge from the Edewechterdamm wastewater treatment plant, which treats wastewater from the city of Bremen. The samples were taken in PVC liners. dried. pulverized, extracted, and analyzed. Samples were taken at different depths in order to analyze sludges of different ages. as noted in Table 3. It was possible to calculate the approximate ages of the sludge samples by evaluating the sludge
(t;onlinu~don pog~ 32)

32 SURFACTANTS
--6- Me .. un:d
..... ~

& DETERGENTS
sediment versus those calculated to be in the sediment if no biodegradation were to occur. Notice the large difference at the 12- and 25-kilometer sampling points . Takada and coworkers (16) studied the fate of LAS in sediments of the Tokyo Bay system. They measured the concentrations of LAS in the rivers feeding the bay, the upper and lower estuaries, and the bay itself. They found that >99.99% of the LAS discharged to the rivers was removed by the time it was transported to the bay. The final example is a worst case situation. In northern Wisconsin, USA, near a small town called Summit Lake is a laundromat operation. The discharge from the laundromat goes into a natural depression which has resulted in the fonnation of a permanent pond and wetland ecosystem shown in Figure 2. Although the pond system has been exposed to high concentrations of detergent chemicals for more than 25 years, significant concentrations of LAS have not been detected in any of several monitoring wells drilled in the area. Work was done to show that soil collected beneath the laundromat pond still had LAS biodegradation capabilities even though it was assumed that the soil would have been anaerobic. The removal of LAS with soil depth beneath the laundromat pond is shown in Figure 3 as LAS decreased from >200 ~g/g to <2 Ilg/g over a vertical distance of less than 3 meters (17). The samples were collected by drilling to various depths, and cores were removed with specialized sampling apparatus to avoid cross contamination. The samples were frozen, shipped to the laboratory, extracted. and analyzed for LAS. These four examples demonstrate that a surfactant such as LAS that would fail the ECETOC No. 28 test is being biodegraded and removed in socalled anaerobic environments such as sediment. landfills, and deep soils. Therefore, this test method does not simulate many of the anaerobic environments of the world. Laboratory work by Larry Britton and colleagues (18.19) provides an explanation why LAS degrades in these apparently anaerobic environ-

""ter (IIIVL) COk:uJ ...... lledi nl (111"1) Meuured Kdi nl (jI.fl)

.1

I
Sampling location in ,,,....{tm)

FIgure 1. Calculated and measured dlsappearal'lC8 of linear alkylbenzane

sulfonate (LAS)

In river water and aedlmenla (continued/rom page 30)

deposition records of the wastewater treatment plant. Over a 14-year period, the concentration of LAS in the sludge decreased by >97% (14). Another striking example of the biodegradation of LAS in a so-called anaerobic environment is shown in Figure I. taken from the work of larson and colleagues (15). This study

was carried out downstream of the Rapid City, South Dakota. USA, wastewater treatment plant which discharges into Rapid Creek. Rapid Creek is a mountain stream whose flow is regulated by the Pacrola Dam some 32 kilometers upstream of Rapid City. It flows 100 kilometers downstream from Rapid City to the Cheyenne River. The only discharge

into Rapid Creek comes from the Rapid City wastewater treatment plant, a trickling filter plant. Monitoring sites were at 0.8, 12, 25. and 48 kilometers downstream of the plant. During the fall sampling period, grab water samples were collected from midchannel and sediment samples from nearshore locations. The data reported here came from a sampling exercise in which the samples were collected in a time sequence based on flow velocity. so that a single volume element of water could be followed downstream. The samples were immediately frozen. shipped to the laboratory, extracted, and analyzed. The major point of this figure is that there is a large difference when a comparison is made between the concentrations of LAS measured in the

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INFORM. \-tlI. 8. no. 1 (January 199n

33

Monitoring well

./

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!
Clay

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mat

./

Laundromat pond

Clay

Organic floc

Sandy vadose zone

--H---------------~--------------~~~~
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, ,

~,

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dlagrlm showlng the maJOI'" environmental eonlpertmentl 01 the Summit lake Laundromat pond system

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flow

Agure 2. Sen-matlc

ments. In the test (test set-up shown in Figure 4), 75 mL sediment slurry was placed in a vessel with smallbore Teflon tubing distributed through it. The lest vessels were 150mL glass serum bottles with grey
butyl rubber septa. The amount of

aeration going to the sediment was

regulated by controlling the flow rate of oxygen through the tubing. Oxy-

gen was introduced into the test vessels by diffusion through Teflon-type polytetrafluroethylene (PTFE) tubing of various lengths. Each flask was filled with a 2-mL high-density polyethylene centrifuge tube containing I.5 mL of 0.25 M KOH to trap any CO2 produced by the sediment microorganisms. {l4C] - benzene ring-labeled CI2 LAS was added at 5 ppm (I x 106 dpm). In this experiment. the flow rate of oxygen was reduced to the point that the rate of oxygen consumption by the sediment was greater than the rate of oxygen coming into the system or. in other words. the environment would be

called anaerobic even though oxygen was still coming into it. Even in this apparent anaerobic environment. LAS underwent complete biodegradation and mineralization (conversion into CO2), The results are illustrated in Figure 5. Furthermore, additional studies by Salanitro and Diaz (20) have demonstrated that the concentrations of surfactants required by the ECETOC No. 28 test method are toxic to sludge and do nor reflect the levels actually found in anaerobic digester sludge. Based on the pattern of use. the major environmental compartments exposed to surfactants are primarily aerobic. Chronic exposure to anaerobic conditions is limited and not likely to significantly impact environmental concentrations. To illustrate the importance of aerobic biodegradation in controlling the environmental fate of surfactants, a mass balance for LAS can be constructed for the United States. In the United States. 75% of LAS is treated in municipal

wastewater treatment systems and about 25% in on-site treatment systems such as septic tank systems. Of the fraction going 10 municipal treatment systems. -77% is removed by mineralization and 22% is sorbed to sludge which is disposed of via incineration. addition to soils. or landfills. LAS associated with sludge continues to undergo extensive aerobic biodegradation in surface soils and, as discussed earlier, will undergo slow but significant biodegradation in landfills. Of the fraction going 10 septic tanks, only 5% is mineralized. 22% is sorbed to sludge, and the remaining 73% is discharged to subsurface soils where extensive aerobic biodegradation has been confirmed. The septic tank sludge is disposed of in municipal treatment systems or applied to soils where continued aerobic biodegradation occurs. The net result is that over 99% of the LAS added 10 the environment has been removed by aerobic mechanisms
( 10).
INFORM. Vol. 8. no. 1 (JonUOf)' 1997)

34

SURFACTANTS & DETERGENTS

test compounds during the tests. These tradeoffs can lead to potential false positive or negative results. For example, surfactant concentrations in most standard biodegradation leSIS range from JO to 100 mgIL so that simple analytical procedures for the surfactants can be utilized. Unfortunately, these concentrations may be toxic to the natural bacterial populations used in the tests. Many times Ihis is due 10 the fact thai the environmental concentration of the surfactant may be orders of magnitude lower that the test concentrations. Larson and his colleague (21,22) demonstrated this effect with LAS in river die-away tests utilizing Ohio River water in which the natural concentration of LAS was measured to be 50 ~gIL but tests were done at 5, 10, 20, 40, and 80 mglL. Not surprisingly. no activity was noted at 20. 40. and 80 mgIL because of toxicity. Biodegradation occurred at 5 and JO mgIL but only after lag limes of al least four days. Only when the rests were done at 50 Ilg/L did biodegradation begin immediately (21.22). A second critical issue is the use of "acclimated" and "nonacclirnated' microorganisms in the tests. As described above. if microorganisms are exposed to certain levels of a surfactant in the environment but tested at much higher concentrations in the test method without being acclimated to the higher concentration, negative results will likely be observed even if it is biodegradable at environmental concentrations. However, many times the microorganisms can "acclimate" to the higher test concentrations and demonstrate adequate biodegradation even at the unrealistically high test concentrations. An important example of this is encountered in doing the presumptive test for LAS in the ASTM Test Method 0-2667-89. "Standard Test Method for Biodegradability of Alkylbenzene Sulfonate" (23). This method states that the test must be done at 30 mglL. It has been documented (24) that only in very concentrated row sewage could 30 mgIL LAS be encountered in the environment. It is very clear that when this method
[continued on pag~36)

'"
o
Agure a. Decrease In LAS concentrations beneath the laundromat pond system as a lunction 01 depth In soli samples collected

+--0,

+--0,
Initial JlWlCof ~I with N2 to create anxrobic conditiom

4111

NIUTOWbon:. ihin,,-all PTFE tubing

4111

Stir bar

150 mL seplum sealed serum bottle

Figure 4. Oxygen diffusion lest vessel

The risk assessment approach teaches us several facts about surfactarns. such as LAS, which may not pass a laboratory anaerobic test: (a) aerobic conditions dominate in the environment, and aerobic biodegradation accounts for >99% removal of LAS; (b) many environments which were assumed to be anaerobic actually do have oxygen penetrating them which allows for aerobic metabolism to continue: and (c) the trace quantities of LAS which may be found in strict anaerobic environments such as deep and undisturbed
INFORM. Vol. 8. no. I {January 199n

sediments are well below those levels having adverse ecotoxicotogicnl impacts. Undue reliance on screening biodegradation tests To understand the significance of results from laboratory biodegradation tests. it is important to remember thai every biodegradation test is a series of tradeoffs between an attempt to simulate some environmental compartment (such as a surface water) and the practical concerns of setting up the test and analyzing the disappearance of

36

SURFACTANTS Be DETERGENTS
20.000 18.000 16.000
~ 14,000

f-

-;

1
e

12.000 10 000 . 8.000

with enough time. activated sludge cultures could be acclimated to 30 mg/L LAS so that positive results would be obtained (Allen M. Nielsen, Condea Vista Company, unpublished
report).

~ 6,000
0,000

'000 0 0 20

~
<0 60
OJ

-"""'"
'20

"'0

,<0

'60

Time(houn) Agure 5. Minefllilution 01 LAS under Manaeroblc~conditions (oxygen cGnlumptlon grealer than oxygen diffusion)

(continued from IKlge 34) was developed in the 1960s, this concentration was selected because of analytical considerations, and this is not an environmentally realistic con-

centration. Also, recent experience has demonstrated thai negative results usually occur with this test if this concentration is used. However. some years ago it was demonstrated that

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INFORM. Vol. 8. no. 1 (January 1997)

1141

To correct this problem, the ASTM subcommittee E47.06 has revised Method D-2667 and changed the concentration from 30 mgfL to 10 mg/L. Data developed by the subcommittee confirmed that this change would alleviate the problem so that reliable positive results could always be obtained with the reference materials. The revised method is in publication. The best approach to doing laboratory biodegradation tests is a tiered approach as recommended by the DECD Expert Group on Degradation and Accumulation (25). The objective of this approach is to provide a system which allows for preliminary screening of chemicals, using relatively simple tests. in order to identify those chemicals for which more detailed and more costly studies are needed. The screening tests are then followed by more definitive but consequently more complex and costly tests. The three tiers are: ready biodegradability, inherent biodegradability, and simulation tests. The ready biodegradability tests are designed to provide limited opportunity for biodegradation in waterbased media using "nonacclimated" microbial populations. If a positive result is obtained, it can be assumed that the test chemical will rapidly biodegrade in the environment. However, as stated by the Expert Group, "A negative result does not necessarily mean that the chemical will not be biodegraded under relevant environmental conditions, but that it will be necessary to progress to the next level of testing." The inherent biodegradability tests are designed to assess whether the chemical has any potential for biodegradation. These tests allow for prolonged exposure of the test compounds to microorganisms, higher concentrations and diversities of microorganisms, rich media, and other conditions which may favor biodegradation. Positive results indi-

37

cate that the chemical will not persist in the environment. In those cases where a more accurate estimate of environmental concentration is required to ensure that undue risk to the environment does not occur. it may be necessary to proceed to the next level and do simulation tests. A negative result will normally mean that further work on biodegradability is not necessary and that persistence may be assumed. Simulation tests are designed to provide evidence of the rate of biodegradation under some environmentally relevant conditions. These tests are more expensive because they usually entail extensive research and may require \t4CJ_ radiolabeled test compounds. Furthermore, even if the very best simulation possible is used. as a general rule the results from laboratory tests underestimate what happens in nature (15.26). In summary. screening biodegradation tests underestimate the biodegradation potential of many compounds including surfactants because of the use of unacclimated microbial populations and unrealistically high test concentrations. Furthermore. even if the best simulations of the environmental compartment of interest are done. these laboratory tests will almost always underestimate the biodegradation capabilities of the real world. Therefore. the use of screening level biodegradation tests to make decisions concerning the environmental fate of a surfactant will likely be grossly overconservanve and eliminate useful surfacrants from the marketplace. Finally. it is evident that the rigid approach to decision-making based only on laboratory test results is not the best. The best approach is to measure or estimate the levels of a surfactant in the environment and compare that 10 the levels at which it causes effects on biological occupants of the environmental compartment in question. Acknowledgments This paper was presented at the 1st Seminar and Exposition on Surfac-

tams. HOUSEHOLD

'96. Brazil. Sao Paulo, Brazil, held June 24-25. 1996. References I. Yamane. L Detergent Raw Materials and Ecologies in Japan, Proceedings of the 3rd CESIO International Surfoctoms Congress & Exhibitioll-A World Market, Plenary Lectures. A & B. London. United Kingdom. June 1-5. 1992. pp. 15-38. 2. Hovetmann. P.. The Basis of Detergents: Basic Oleochemicals. Proceedings of the 3rd World Conference on Detergents: Global Perspectives. edited by Arno Cahn. AOCS Press. Champaign. IL, 1994. pp. 117-122. 3. Satsuke. T.. Methyl Ester Sulfcnares: A Surfactant Based on Natural Fats, Ibid .. pp. 135-140. 4. Tenside Surfactant Detergents 32(2).-82-193 (1995). 5. Stalmans M . H. Berenbold. J.L. Bema, L. Cavalli. A. Dillarstone. M. Franke. F. Hirsinger. D. Janzen. K. Kosswig. D. Postlethwaite. T. Reppert. C. Renta. D. Scharer. K.-P. Schick. W. Schul. H. Thomas. and R. Van Sioten, European Life-Cycle Inventory for Detergent Surfactant Production. Ibid.:84-109 (1995). 6. Feijtel, T.C.J .. and E.1. van de Plassche. Environmental Risk Characterization of 4 Major Surfoctonts Used in TIle Netherlands, Report 679101-025. National Institute of Public Health and Environmental Protection and Dutch Soap Association. September 1995. 7. The Commission of the European Communities. Commission Decision of 25 July 1995. Establishing the Ecological Criteria for the Award of the Community Ecolabel to Laundry Detergents. Official loumal of the European Commanates. Sept. 13. 1995, pp. 14-30. 8. United Kingdom Department of the Environment. 2nd Report of the Technical Comminee on Detergents and the En"ironmellf. 1994, pp. 53-60. 9. Nordic Environmental Labeling, Environmental Labeling of Deter-

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gents for Textiles. Detergents 0613.1. Feb. 2. 1996. Birch. R.R., W.E. Gledhill, R.J. Larson, and A.M. Nielsen. Role of Anaerobic Biodegradability in the Environmental Acceptability of Detergent Materials. Proceedings of the 3rd CESIO International Surfoaants Congress & r:hibitiOll-A \Vorld Markel. Sessions . F & LCA Seminar, London, United Kingdom, June 1-5, 1992, pp. 26-33. European Chemical Industry Ecology and Toxicology Centre (ECETOC), Evaluation of Anaerobic Biodegradation, Technical Report No. 28. Brussels, June 1988. Pfennig, N., Formation of Oxygen and Microbial Processes Establishing and Maintaining Anaerobic Environments, In Strategies of Microbial Life ill Extreme Environments. edited by M. Shilo. Dahlem Konferenzen, Berlin, 1979, pp. 137-148. Schobert. P., Basic Principles of LAS Biodegradation. Tenside Surfactant Detergents 26(2): 86-94 (1988). Marcomini. A . F. Cecchi, and A. Sfrisco, Analytical Extraction and Environmental Removal of Alkylbenzene Sulphonates. Nonylphenol and Nonylphenol Monoerhoxytate from Dated Sludge-Only Landfills. Environ. Tech. 12:1047-1054(1991). Larson. R.J .. T.M. Rothgeb. R.J. Shimp, T.E. Ward. and R.M. Ventullo. Kinetics and Practical Significance of Biodegradation of Linear Alkylbenzene Sulfonate in the Environment. J. Am. Oil Chem. Soc. 70:645-657 (1993). Takada. H., R. Ishiwatari, and N. Ogura. Distribution of linear Alkylbenzenes (LABs) and Linear Alkylbenzene Sulphonates (LAS) in Tokyo Bay Sediments. Estuarine. Coastal and Shelf Science 35:141-156 (1992). Larson. R.J .. T.W. Federle. R.J. Shimp. and R.M. Ventullo. Behavior of Linear Alkylbenzene Sulfonate (LAS) in Soil Infiltrauon and Groundwater. Tenside Surfactant Detergents 26 (2),116-121(1989). Britton. L.N .. and A. M. Nielsen. Relevance of Anaerobic Biodegradability Testing to Environmental Fate. Abstract I02P. First SETAC World Congress, Ecotosicology and Environmental Chemistry-A Global Perspective. Lisbon. Portugal. March 28-31. 1993. Heinze. J.. and L.N. Britton. Anaerobic Biodegradation: Environmental Relevance, Proceedings of the 3nl World Conference on Detergents: Global PerSIJeCrives, edited by Arno Cahn. AOCS Press. Champaign, IL. 1994. pp. 235-239. Satanuro. J.P .. and L.A. Diaz. Anaerobic Biodegradability Testing of Surfactants, Chemospilere 30(5),813-830 (1995). Larson. R.J., Comparison of Biodegradation Rates in laboratory Screening. Studies with Rates in Natural Waters, Residue Reviews 85: 159-171 (1983). Larson. R.J.. and R.L. Perry. Use of the Electrolytic Respirometer to Measure Biodegradation in Natural Waters. \Valer Research IH97-702 (1981). ASTM Designation: D 2667-89. Standard Test Method for Biodegradability of Alkylbenzene SUlfonate. Annual Book of ASTM Standards, Vol. 11.05, ASTM. West Conshohocken. Pennsylvania. Painter. H.A., and T.F. Zabel. Review of the Environmental Safety of LAS. WRc Report CO /659-M/I/EV 8658, The European Centre of Studies on Linear Alkylbenzene and Derivatives (ECOSOL). 1988. OECD Guidelines for Testing of Chemicals. Section 3: Degrodonon and Accumulation. Summary of Consideration, Paris, May 12. 1981. pp. \-5. Schroder. F.R.. Concentrarions of Anionic Surfactants in Receiving Riverine Water, Tenside Surfactallt Oetergents 32(6):492-497 (1~5).

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