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Journal of Oleo Science Copyright ©2008 by Japan Oil Chemists’ Society J. Oleo Sci. 57, (10) 529-538 (2008)

J ournal of Oleo Science Copyright ©2008 by Japan Oil Chemists’ Society J. Oleo Sci. 57

Aquatic Toxicity and Biodegradability of Advanced Cationic Surfactant APA-22 Compatible with the Aquatic Environment

Masayuki Yamane 1 , Takamasa Toyo , Katsuhisa Inoue 2 , Takaya Sakai 2 , Youhei Kaneko 2 and Naohiro Nishiyama 1

1 Safety Science Research Laboratories, Kao Corporation (2606 Akabane, Ichikai machi, Haga-gun, Tochigi 321-3497, JAPAN) 2 Material Science Research Laboratories, Kao Corporation (1334, Minato, Wakayama-shi, Wakayama 640-8580, JAPAN)

1

Abstract: Cationic surfactant is a chemical substance used in hair conditioner, fabric softener and other household products. By investigating the relationship between the aquatic toxicity and the chemical structures of two types of mono alkyl cationic surfactants, alkyl trimethylammonium salts and alkyl dimethylamine salts, we have found that the C22 alkyl chain length is effective to reduce the toxicity. Besides, we have recognized that the amidopropyl functional group contributes to the enhanced biodegradability by investigating the biodegradation trend of (alkylamidopropyl)dimethylamine salt (alkyl chain length: C18). Based on these findings, we have developed mono alkyl cationic surfactant called APA- 22, N-[3-(dimethylamino)propyl]docosanamide salt. APA-22 is formed by the C22 alkyl chain, amidopropyl functional group and di-methyltertiary amine group. We evaluated the aerobic and anaerobic biodegradability of APA-22 by two standard methods (OECD Test Guideline 301B and ECETOC technical document No.28) and found that this substance was degraded rapidly in both conditions. The toxicity to algae, invertebrate and fish of this substance are evaluated by using OECD Test Guideline 201, 202 and 203, respectively. All acute toxicity values are >1 mg/L, which indicates that environmental toxicity of this substance is relatively less toxic to aquatic organism. In addition, we estimated the biodegradation pathway of APA-22 and observed the complete disappearance of APA-22 and its intermediates during the test periods. Based on the environmental data provided above, we concluded that APA22 is more compatible with the aquatic environment compared to other cationic surfactants with mono long alkyl chain.

Key words: mono alkyl cationic surfactant, biodegradation, aquatic toxicity, environmental compatibility

1 INTRODUCTION

Cationic surfactant is an important chemical substance and used for wide variety of hair conditioner, fabric soften- er and other household products. Therefore, cationic sur- factant should be biodegradable and less toxic to aquatic organisms. In addition, it is becoming more important to develop a chemical substance with environmental compati- bility, since chemical management such as REACH (Regis- tration, Evaluation, Authorization of Chemicals), Detergent Regulation in EU and GHS (Globally Harmonized System) are getting more attention these days. Some cationic sur- factants mainly used in fabric softener, such as esterquat,

DEEDMAC and esteramide, are known as biodegradable and less toxic to aquatic organisms 1-4) . However, some of the mono alkyl cationic surfactant is not-readily biodegrad- able and toxic to aquatic organisms. Masuda et al. reported that alkyl trimethylammonium chloride (TAC) with C18 alkyl chain tends to be not-readily biodegradable because of its inhibition for microorganisms 5) . Aquatic organisms appear to be sensitive to cationic surfactant, and the toxic- ity of alkyl trimethyammonium bromide and alkyl trimethylammonium chloride to algae is characterized by EC50 below 1 mg/L 6) . LC50/EC50 of some TAC to inverte- brate and fish is also reported below 1 mg/L 7,8) . Besides,

Correspondence to: Masayuki Yamane, Safety Research Laboratories, Kao Corporation, 2606 Akabane, Ichikai machi, Haga-gun, Tochigi 321-3497, JAPAN E-mail: Yamane.masayuki@kao.co.jp Accepted June 20, 2008 (received for review May 13, 2008)

Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online http://www.jstage.jst.go.jp/browse/jos/

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M. Yamane, T. Toyo, K. Inoue et al.

OECD SIDS report summarized that one of the alkyl dimethylamine salt (DMA), named N,N-dimethyldodecy- lamine, is also toxic to the aquatic organisms, whose toxic- ity to algae, daphnia and fish is below 1 mg/L 9) . Most of the previous studies concluded that mono alkyl cationic sur- factant tends to have adverse effect to the aquatic organ- isms and not-readily biodegradability when its alkyl chain length increases. It is important to develop mono alkyl cationic surfactants with no adverse effect to aquatic organisms. Nevertheless, the study about developing the eco-friendly mono alkyl cationic surfactant has not shown much progress during the last decade. In order to develop the modified mono alkyl cationic surfactant compatible with the environment, we investigated the relationship between the chemical structures of the cationic surfac- tants and their environmental properties (biodegradation and aquatic toxicity). At first, we conducted the study to find the relationship between alkyl chain length and the environmental properties by comparing biodegradability and toxicity of TAC and DMA. Second, we tried to find the effect of intermediate functional group on the biodegrad- ability and toxicity of the surfactants. On the basis of the above evaluations, we developed mono alkyl cationic sur- factant, named APA-22, N-[3-(dimethylamino)propyl] docosanamide salt (AMIDET ® APA-22, Kao Chemicals Europe, S.L.) whose surfactant property is excellent 10) . This substance consists of C22 alkyl chain, amidopropyl functional group and di-methyl tertiary amine group. We investigated the environmental compatibility of APA-22 by evaluating its biodegradation, aquatic toxicity and biodegradation pathway.

2 EXPERIMENTAL

2.1 Materials

Mono alkyl cationic surfactants used in this study are alkyl trimethylammonium chlorides (TAC, alkyl chain length: C12, C14, C16, C18, C22, C24), alkyl dimethylamine lactic acids (DMA, alkyl chain length: C12, C14, C16, C18, C20, C22) and (alkylamidopropyl)dimethylamine lactic acid (APA, alkyl chain length: C18 and C22). Only APA-22 has the distribution of alkyl chain length from C18 to C24. The other surfactants reported in this study have no chain length distribution. The chemical names, structures, abbreviations and purity are shown in Table 1. These sur- factants are synthesized by the Material Science Research Laboratories, Kao Corporation, Wakayama, Japan.

2.2 Evaluation of biodegradation and aquatic toxicity

The test condition details of biodegradation and aquatic toxicity are shown in Table 2. The biodegradation of TAC- 18, TAC-20, TAC-22, TAC-24, DMA-22 and APA-18 is eval- uated based on OECD Test Guideline (OECD TG) 301C 11) as

followings. Usually, OECD TG 301C guideline recommends that the concentrations of substance and standard activat- ed sludge are 100 mg/L and 30 mg/L, respectively. In this particular study, the concentration of substance and acti- vated sludge collected from wastewater treatment plant are 15 mg/L and 50 mg/L, respectively, to avoid the inhibitory effect of these substances to microorganisms. The biodegradability is calculated from Biochemical Oxy- gen Demand (BOD). Biodegradation of DMA-12, DMA-14, DMA-16, DMA-18, DMA-20 and APA-22 are evaluated by OECD TG 301B 11) , where the concentrations of substance and activated sludge are 10 mgC/L and 30 mg/L, respec- tively, and biodegradability is calculated from evolved CO 2 . The concentration of test materials and activated sludge of OECD TG 301B and 301C used in this study is similar to each other. Therefore, we can regard that biodegradation of these surfactants is evaluated in a similar condition. In addition, anaerobic biodegradation of APA-22 is evaluated by the ECETOC technical document No. 28. BOD and Dis- solved Organic Carbon (DOC) are analyzed by following devices. BOD is measured by the coulometric oxygen uptake recorder, OM3001 (Ohkura Electric Co. Ltd). DOC is measured by the Total Organic Carbon analyzer, TOC- 5000A (SHIMADZU CORPORATION). The biodegradabili- ty value in Table 3 shows the average value (n=2). Aquatic toxicity to algae, daphnia and fish of TACs (C12, C14, C16, C18, C22), DMAs (C12, C14, C16, C18, C22) and APAs is evaluated by OECD TG 201 12) , 202 13) and 203 14) , respectively. The eco-toxicity was calculated based on the nominal concentration except for APA-22.

2.3 Estimation of biodegradation pathway of APA-22

In order to estimate the biodegradation pathway of APA- 22, biodegradation test using the river water is also evalu- ated. The river water was collected from Tagawa-river in urban area of Utsunomiya, Tochigi prefecture, Japan. The

intermediates originated from APA-22 in the river water were analyzed by proton Nuclear Magnetic Resonance ( 1 H- NMR) to identify their chemical structures, and DOC was also analyzed at several sampling points to monitor the reduction of organic matter. Test concentration of APA-22 set up to 30 mg/L in order to cover the limit of quantity (LOQ) of DOC, though this concentration is relatively high compared to the major surfactants monitored in urban rivers in Japan 15) . River water of 400 ml sampled at 5-day and 19-day is freeze dried up and dissolved in CD 3 OD solu- tion of 3 mL. 1 H-NMR of river water is measured by using of Mercury-400 (Varian Corporation) in the method of non- decouple mode at the room temperature.

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Structure

Chemical Names, Abbreviations, Purity and Structures of TAC, DMA and APA.

Purity (%)

97.8
98.4

98.0
97.0

99.7
99.6

98.3
99.2

98.5
98.9

98.7

95.7

99.7

98.5

The weight percentage of alkyl chain length of APA-22 is followings; C18/C20/C22/C24 = 2.6%/6.8%/87.0%/1.7%. The other materials have no distribution of alkyl chain.

Abbreviation

DMA-14

DMA-16

DMA-12

DMA-22

DMA-18

APA-22

TAC-24

TAC-14

TAC-20

APA-18

TAC-16

TAC-22

TAC-12

TAC-18

N-[3-(dimethylamino)propyl]octadecanamide lactic acid salt

N-[3-(dimethylamino)propyl]docosanamide lactic acid salt

Chemical name

Table 1

Dodecyl-N,N,N-trimethylammonium chloride Tetradecyl-N,N,N-trimethylammonium chloride Hexadecyl-N,N,N-trimethylammonium chloride Octadecyl-N,N,N-trimethylammonium chloride Icosyl-N,N,N-trimethylammonium chloride Docosyl-N,N,N-trimethylammonium chloride Tetracosyl-N,N,N-trimethylammonium chloride

N,N-Dimethylhexadecylamine lactic acid salt N,N-Dimethyloctadecylamine lactic acid salt N,N-Dimethyldocosylamine lactic acid salt

N,N-Dimethyldocecylamine lactic acid salt N,N-Dimethyltetradecylamine lactic acid salt

Aquatic Toxicity and Biodegradability of Advanced Cationic Surfactant APA-22

Aquatic Toxicity and Biodegradability of Advanced Cationic Surfactant APA-22 J. Oleo Sci . 57 , (10)
Aquatic Toxicity and Biodegradability of Advanced Cationic Surfactant APA-22 J. Oleo Sci . 57 , (10)
Aquatic Toxicity and Biodegradability of Advanced Cationic Surfactant APA-22 J. Oleo Sci . 57 , (10)

J. Oleo Sci. 57, (10) 529-538 (2008)

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Table 2

Test Condition of Biodegradation and Aquatic Toxicity. To avoid the inhibitory effect of substances to microorganisms, concentrations of test material and activated sludge of OECD301C (modified) are 15 mg/L and 50 mg/L, respectively.

Biodegradation

OECD301C (modifed) Source of inoculum

Activated sludge (Moka sewage treatment plant)

Material concentration

15

mg/L

Activated sludge concentration

50

mg/L

Volume of nutrient medium

300 mL

Test periods

28

days

Measured parameter

BOD, DOC

OECD301B

Source of inoculum

Activated sludge

Material concentration

10

mgC/L

Activated sludge concentration

30

mg/L

Volume of nutrient medium

3000 mL

Test periods

28

days

Measured parameter

Evolved CO 2

Algae inhibition test (OECD201)

Species:

Desmodesmus subspicatus (CCAP276/20)

Pseudokirchneriella subcapitata (CCAP278/4)

Incubation time:

72

hours

Irradiation:

65

uEm 2 /s, continuously

Temperature:

22

End point:

Growth rate (ErC 50 )

Daphnia sp., acute immobilisation test (OECD202)

Species:

Daphnia magna

Incubation time:

48

hours

Irradiation:

Light/Dark=16/8 hours

Temperature:

20

End point:

Immobilisation (EC 50 )

Fish acute toxicity test (OECD203)

Species:

Oryzias latipes (Himedaka)

Incubation time:

96

hours

Irradiation:

Light/Dark=16/8 hours

Temperature:

25

End point:

Mortality (LC 50 )

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Aquatic Toxicity and Biodegradability of Advanced Cationic Surfactant APA-22

3 RESULTS

3.1 Biodegradability of tested materials

Table 3 shows the biodegradability of TACs (C18, C20, C22 and C24), DMAs (C12, C14, C16, C18 and C22) and APAs (C18 and C22). BOD of TACs ranges from 0 % (C22 and C24) to 40 % (C18). Degradability of DMAs calculated from evolved CO2 and BOD ranges from 32 % to 100 % (Table 3). The degradability of TAC and DMA with short alkyl chain tends to be better than that of long alkyl chain. The degradation of APA-18 and APA-22 are 93 % and 100 %, respectively. DMA-12, DMA-16 and APA-22 also passed the criteria of 10 day-windows as readily biodegradable. Anaerobic biodegradability of APA-22 evaluated by stan- dard procedure is also 100%.

3.2 Aquatic toxicity of tested materials

The acute toxicity of TACs (C12, 14, 16, 18, 22) and DMAs (C12, 14, 16, 18, 22) is shown in Fig.1. The acute tox- icity (ErC50) of TACs and DMAs to algae ranges from 0.0092 to 0.52 mg/L, and most toxic alkyl chain of TAC and DMA are observed at C14 and C16, respectively. The acute toxicity (LC50) of TACs and DMAs to fish ranges from 0.11 to 22 mg/L, and most toxic chain length of TAC and DMA are observed at C18 and C16, respectively. The acute toxic- ities (EC50) of TAC-22 and DMA-22 to daphnia are 0.044 and 0.97 mg/L, respectively. Figure 2 summarizes the acute toxicity of APAs. The acute toxicity of APA-18 to

algae, daphnia and fish ranges from 0.08 to 0.30 mg/L. All acute toxicity of APA-22 is over 1 mg/L, ranging from 1.4 to 6.6 mg/L.

of APA-22 is over 1 mg/L, ranging from 1.4 to 6.6 mg/L. Fig. 1 T oxicity

Fig. 1 Toxicity Profile of TACs and DMAs to Algae (top) and Fish (bottom). Toxicities are calculated based on the nominal concentration. The toxicity of TAC-22 and DMA-22 to daphnia is 0.044 mg/L and 0.97 mg/L, respectively (It is not shown in Fig. 1).

Table 3

Biodegradability of TACs, DMAs and APAs. Degradability evaluated by OECD301C is calculated from BOD. That of OECD301B is based on the evolved CO 2 . Degradability shows the average value (n=2).

Test sample

Alkyl chain

Protocol

Degradability (%)

 

18

OECD301C (modified)

40

TAC

20

OECD301C (modified)

14

22

OECD301C (modified)

0

24

OECD301C (modified)

0

 

12

OECD301B

72

14

OECD301B

59

DMA

16

OECD301B

100

18

OECD301B

49

22

OECD301C (modified)

32

APA

18

OECD301C (modified)

93

22

OECD301B

100

DMA-12, DMA-16 and APA-22 also satisfied the 10 day-window criteria as readily biodegradable.

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M. Yamane, T. Toyo, K. Inoue et al.

M. Yamane, T. Toyo, K. Inoue et al. Fig. 2 T oxicity of APA-18 and APA-22

Fig. 2 Toxicity of APA-18 and APA-22 to Algae, Daphnia and Fish. Toxicities of APA-22 are calculated from the measured concentration.

4 DISCUSSION

4.1 Biodegradation trend of tested mono alkyl cationic sur- factants The biodegradation of TACs is below 50% despite of evaluating at low test concentration (15 mg/L). Especially, BOD of TAC-22 and TAC-24 is 0 %, which shows that TAC with long alkyl chain is not easily biodegradable. This trend is similar to the previous study. Masuda et al. report- ed that the biodegradability of octyl and decyl trimethyl ammonium chloride (TAC-08 and TAC-10) is over 60%, while TAC with long alkyl chain length decreases degrad- ability 5) . No degradation of TAC-22 and TAC-24 suggests the occurrence of inhibition to microorganisms. On the other hand, the degradability of DMA-12 and DMA-16 is over 70% and passed the 10 day-window criteria, indicat- ing that DMAs with short alkyl chain are readily biodegradable. Besides, OECD SIDS report summarized N,N-dimethyldodecylamine is readily biodegradable 9) , which is consistant with our data showing short alkyl chain is more degradable. DMA-18 and DMA-22 show degradability below 50%. As discussed in biodegradation of TACs, DMA with long alkyl chain may also inhibit the oxy- gen consumption by microorganisms. However, DMAs with long alkyl chain have a potential of biodegradation as indicated by their degradability ranging from 32 % to 49 %. Based on the relationship between alkyl chain length and biodegradability of TACs and DMAs, we can conclude that (i) DMA is relatively more biodegradable than TAC, and (ii) short alkyl chains are more favorable for biodegradation than long alkyl chains. On the other hand, differently from the trends of TACs and DMAs, the biodegradability of APA-18 is over 90 %, and that of APA-22 is also 100 % and passed the 10 day-window criteria. Furthermore, anaero- bic biodegradability of APA-22 is also 100 %, which indi- cates that APA-22 is completely degraded into the minerals by microorganisms in the anaerobic conditions. They have a long alkyl chain. Nevertheless, biodegradability is excel-

lent. This indicates that the amidopropyl functional group contributes to the enhanced biodegradability.

4.2 The relationship between aquatic toxicity and the

structure The toxicity profile of TACs and DMAs to algae, daphnia and fish is shown in Fig. 1 as a function of alkyl chain length of the surfactants. The acute toxicity of TAC and DMA to algae shows a parabolic trend. The most severe toxicity of TAC and DMA to algae is observed at C14 and C16 alkyl chain, respectively. The acute toxicity (LC50) of TACs and DMAs to fish also shows a parabolic trend. The lowest toxic value of TAC and DMA is observed at C18 and C16 alkyl chain, which indicates that toxic effect is severe around C16 and C18 alkyl chain. These parabolic trends suggest that the toxicity of mono cationic surfactant is not simply related to the length of alkyl chain, but there is a maximum point of toxicity. Dyer et al. have developed the quantitative structure-activity relationships (QSAR) of anionic surfactant, alcohol ethoxysulphates (AES), based on the chronic toxicity to daphnia. This QSAR calculates the No Effect Observed Concentration (NOEC) of daphnia by the alkyl chain length and number of mole of ethoxylate

of AES 16) . A parabolic trend is also observed in this QSAR, which shows that the most toxic effect of AES to daphnia occurs at C14 and C15 alkyl chain. This supports that alkyl chain length is also a key factor determining the toxicity of mono alkyl cationic surfactants. We have to avoid using the C14, C16 and C18 alkyl chains for developing the mono alkyl cationic surfactant compatible with environment. Based on the relationship between alkyl chain length and aquatic toxicity of TACs and DMAs, we found that aquatic toxicity of TAC and DMA with C22 alkyl chain is relatively less toxic than other alkyl chains. These trends indicate that C22 alkyl chain is compatible with the aquatic toxicity. Though there is not many data, the acute toxicity of DMA-

22 to daphnia tends to be less toxic than TAC-22, which

indicates that toxicological compatibility of DMA is better than TAC. The toxicity of APA-18 to algae and fish shows the same order of toxic values of DMA-18. It suggests that the combination of C18 alkyl chain and amidopropyl func- tional group is not an effective structure for reducing the

toxicity. On the other hand, APA-22 is less toxic than APA-

18 by two orders of magnitude and all toxicity values of

APA-22 to algae, daphnia and fish are over 1 mg/L. As dis- cussed in biodegradation trend, we found that the combi- nation of long alkyl chain and amidopropyl functional group is also very important structure to reduce the aquatic toxi- city.

4.3 Possible biodegradation pathway of APA-22

To investigate the biodegradation pathway of APA-22, structure of intermediate is determined by 1 H-NMR analy-

sis, and residual organic matters are measured by DOC

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Aquatic Toxicity and Biodegradability of Advanced Cationic Surfactant APA-22

analysis. Figure 3 shows the 1 H-NMR chart of APA-22 dis- solved in the CDCl 3 , 5-day and 19-day samples dissolved in CD 3 OD. In the standard solution without inoculums, typi- cal proton signals of C22 alkyl chain, amidopropyl, methyl of amine and lactic acid salt are observed. In 5-day sample, APA-22, fatty acid and N,N-dimethyl-1,3-propanediamine (DMAPA) are clearly detected, while lactic acid is disap- peared completely. This suggests that hydrolysis occurred between fatty acid and DMAPA in the primary biodegrada- tion process. This kind of cleavage has been also reported in biodegradation pathway of di-long-chain tertiary amine

salt 3) . In 19-day sample, APA-22 and fatty acid have com- pletely disappeared, and only DMAPA is observed. Residu- al organic matters (DOC) originated from APA-22 decrease gradually and disappear at 28-day, which indicates that APA-22 and its intermediates are completely removed from tested river water during the test periods (Fig. 4). We have estimated the possible route of biodegradation pathway of APA-22 as shown in Fig. 5. In the primary stage, APA-22 is separated into two intermediates by hydrolysis. One is fatty acid and the other is DMAPA. After hydrolysis, fatty acid is mineralized to CO 2 and H 2 O through the omega and

mineralized to CO 2 and H 2 O through the omega and Fig. 3 1 H-NMR

Fig. 3 1 H-NMR Chart of Standard Solution, 5-day Sample and 19-day Sample. Small alphabetical letters denote the each proton signal for APA-22 and lactic acid. Capital letters and numerals also denote each proton signals for fatty acid and DMAPA.

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M. Yamane, T. Toyo, K. Inoue et al. Fig. 4 Dissolved Organic Carbon (DOC) Profile of

Fig. 4

Dissolved Organic Carbon (DOC) Profile of Residue Organic Matter Originated from APA-22 in Biodegradation Test Using River Water.

from APA-22 in Biodegradation Test Using River Water. Fig. 5 Estimated Biodegradation Pathway of APA-22. This

Fig. 5

Estimated Biodegradation Pathway of APA-22. This pathway is estimated from 1 H-NMR and DOC analysis.

beta-oxidation process. DMAPA is also mineralized to CO 2 , H 2 O, NH 3 , and NO 2 (or NO 3 ). Investigating the biodegrada- tion test of APA-22 using river water, we observed the dis- appearance of APA-22 and its intermediates during the test period.

4.4 Environmental hazardous data of the intermediates originated from APA-22 The toxicity of APA-22 to of algae, daphnia and fish is over 1 mg/L (Table 4), which is relatively less toxic to aquatic organisms than other mono alkyl cationic surfac-

tants. The aquatic toxicity of some intermediates originat- ed from a degradation of APA-22 is reported. Toxicity of C22 fatty acid to algae, daphnia and fish is over 5.0 mg/L and is less toxic than APA-22 17) . Toxicity of DMAPA to algae, daphnia and fish is also less toxic than APA-22 and all toxic values are over 50 mg/L 18) . Besides, C22 fatty acid and DMAPA are also reported to be readily biodegrad- able 18,19) . According to the above hazardous data of interme- diates, it is suggested that there will be a little adverse effect for environmental risk.

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100% (passed the 10 day-window)

69% (Readily biodegradable)

52% (Readily biodegradable)

Result and LC50/EC50Protocol

>5.0 mg/L

>5.0 mg/L

>5.0 mg/L

mg/L

mg/L

122 mg/L

mg/L

mg/L

mg/L

100%

56.2

59.5

1.4
6.6

2.1

Algentest in Anlehnung an UBA

Biodegradability and Aquatic Toxicity of APA-22 and Its Intermediates.

EG-Richtlinie 78/83/EGW DIN 38412

ECETOC T.D. No 28

OECD301D

OECD301C

OECD301B

OECD202

OECD202

OECD203

OECD203

OECD201

OECD201

- Pseudokirchneriella subcapitata

- Pseudokirchneriella subcapitata

- Desmodesmus subspicatus

Species

Oncorhynchus mykiss

-

Daphnia magna

Daphnia magna

Daphnia magna

Oryzias latipes

Leuciscus idus

Table 4

Aerobic biodegradation Anaerobic biodegradation

Test type

Biodegradation

Biodegradation

Invertebrate

Invertebrate

Invertebrate

Algae

Algae

Algae

Fish

Fish

Fish

dimethylamine

C22 Fatty acid

Test substance

Aminopropyl

(DMAPA)

APA-22

Aquatic Toxicity and Biodegradability of Advanced Cationic Surfactant APA-22

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M. Yamane, T. Toyo, K. Inoue et al.

5 CONCLUSIONS

On the basis of the relationship between environmental

detergent builders to Algae: A review and risk assess- ment. Ecotox. Environ. Saf. 20, 123-140 (1990).

properties (biodegradation and aquatic toxicity) and struc- tural characteristics (alkyl chain length and intermediate functional group) of TACs, DMAs and APAs, we have

7.

Cooper, J.C. Review of the environmental toxicity of quaternary ammonium halides. Ecotox. Environ. Saf. 16, 65-71 (1988).

developed the advanced mono alkyl cationic surfactant, APA-22. APA-22 is easily biodegradable in both of aerobic and anaerobic conditions. In addition, the toxicity to algae,

8.

Boethling, R.S. Environmental aspects of cationic sur- factants in Cationic Surfactants, Marcel Dekker Inc. pp.95-130 (1994).

daphnia and fish is over 1 mg/L, indicating that APA-22 is less toxic to aquatic organisms than other mono alkyl cationic surfactants. The combination of C22 alkyl chain

9.

SIDS Initial Assessment Report for SIAM. N,N- Dimethyldodecylamine, http://cs3-hq.oecd.org/scripts/ hpv/

and amidopropyl functional group is very important for the enhanced biodegradation and reducing the aquatic toxicity. Besides, intermediates produced in the degradation by microorganisms are also readily biodegradable and less toxic than APA-22.

10.

Sakai, T.; Inoue, K.; Yamane, M.; Toyo, T.; Nishiyama, N.; Kaneko, Y. The excellent water-solubility of N -[3- (dimethylamino)propyl]docosanamide chloride-The most eco-friendly cationic hair conditioning agent. J. Oleo Sci. 57, 521- (2008).

ACKNOWLEDGMENT

11.

Organisation for Economic Co-operation and Develop- ment. Guidelines for the testing of chemicals: Test guideline 301 Readily Biodegradability ”, OECD, Paris (1992).

We acknowledge for many toxicologists in Safety Research Laboratories, Kao Corporation. They derived the environmental data. And we also acknowledge for Mr Suzuki for useful comments and suggestions.

12.

Organisation for Economic Co-operation and Develop- ment. Guidelines for the testing of chemicals: Test guideline 201 Freshwater Alga and Cyanobacteria, Growth Inhibition Test”, OECD, Paris (2006).

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