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Classification and Labelling of Surfactants

By Frederick Williams,2014-09-28 11:24
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Classification and Labelling of Surfactants

    Classification and Labelling of Surfactants for human health hazards according to the Dangerous Substances Directive

    CESIO recommendations for Anionic and Non-ionic surfactants

     (including 1990 recommendations on Quaternary Ammonium

    Compounds and Fatty Amines and Derivatives)

    January 2000

    Introduction

    1On two separate occasions during the 1980’s, CESIO reviewed company reports of toxicology

    studies on marketed surfactants to provide guidance for classification and labelling in line with the requirements of Annex VI of the Dangerous Substances Directive [DSD] (1). By reviewing all available experimental results, CESIO believed that “weight of evidence” enabled them to provide the most accurate guidance. The first of these reviews was reported in 1984 (2). At this time many of the studies had not been conducted strictly according to developing OECD/EC guidelines (3, 4-Annex V) and for that reason, a second review was undertaken several years later. This was completed in 1990 (5).

    For both reviews, surfactants were grouped into 4 categories (anionics [for convenience this group also contained 3 amphoteric categories], non-ionics, quaternary ammonium compounds and fatty amines and their derivatives) and several sub-categories on the basis of their chemical and physical properties. Acute oral toxicity, skin and eye irritation and skin sensitisation studies were reviewed by an expert task force (TF) and recommendations for classification and labelling were made.

    In 1993, the European Union revised their criteria for classification and labelling of substances and preparations based on their potential to cause ocular lesions (6). Two of these new criteria are very specific for the use of risk phrase R41 (Risk of serious damage to eyes). Additionally, in 1995 new experimental data on the irritation potential of several surfactant raw materials became available, which were considered to be of value for a further refinement of the classification and labelling recommendations given in 1990. Consequently, CESIO established a new TF to review their guidance on the classification and labelling of anionic and non-ionic surfactants. This report describes the objectives of this exercise, the composition of the TF, the process followed, it presents results and updates recommendations for classification and labelling. Only studies conducted according to DSD Annex V methodology were taken account thof in this exercise and interpretation was strictly according to the 18 ATP (6).

    As a result, several classification and labelling recommendations are increased from those currently in place. The implications of these changes are discussed later in this document. For completeness, the tables on quaternary ammonium compounds and fatty amines and derivatives from the 1990 TF report are appended.

    Objectives

    The following terms of references formed the basis of this task:

    1. Review all available studies for acute oral toxicity and skin and eye irritation on anionic

    and non-ionic surfactants that conform to DSD (4) Annex V.

    2. Determine whether existing CESIO classification and labelling recommendations for these

    endpoints are appropriate. Where not, revise recommendations. Classification for eye

    irritation was a particular issue since the previous TF had recommended a risk phrase of R

    36* for surfactants that cause persistent effects on the eye. R 36* is not an official EC

    phrase.

    The Task Force

    The following toxicologists and classification and labelling specialists participated. D Calcinai Condea Augusta ChB Jassogne Cesio

    H Certa Condea Chemie W Kohl Henkel

     1 CESIO = Comité Européen des Agents de Surface et leurs Intermédiaires

    Organiques

    2

W M Clous Akzo Nobel R Kreiling Hoechst, now

    Clariant

    S Dechert Hüls, now Degussa Hüls P A Martin Albright & Wilson

    O-J Grundler BASF B Molinier Elf-Atochem

    B Hendrickx Rhone-Poulenc, now Rhodia RAJ Priston Shell Chemicals

    [chairman]

    G Holland Unilever J-F Regnier Elf-Atochem

    L Hughes ICI Performance Chemicals, now C Verge Petresa

    Uniqema

    The process

    The intent of this TF was to re-assess existing animal studies and to review as many new ones as possible whilst maintaining confidentiality of privileged information. To achieve this, questionnaires, developed for each of the end-points, were completed by participating companies and returned to CESIO secretariat. Confidential information (e.g. product name, company name) was then obscured and the questionnaires were coded before being passed to the TF for review. Questionnaires for each of the end points are shown in appendices 1-3 (skin irritation, eye irritation and acute oral toxicity, respectively). For inclusion in the final assessment, questionnaires were judged on the details provided on the test material and on compliance with current OECD/EC methodology. Adherence to Good Laboratory Practice was not a requisite if the test was otherwise well conducted.

    The assessment was conducted during 2 meetings of the TF. Questionnaires were evaluated and classifications derived using EC criteria (6). Additionally, for some sub-categories and 2particularly for eye irritation, the TF ensured that its conclusions were in line with the ECETOC

    report on eye irritancy (7) and took account of the findings of previous CESIO reviews.

    Results and Discussion

    Existing and proposed classification and labelling recommendations for anionic and non-ionic surfactants are summarised in tables 4 and 5, respectively. Supplementary information is provided in the following paragraphs:

    Questionnaires

    A total of 421 questionnaires (see table 1) were returned from the following companies: Akzo Nobel Goldschmidt Muenzing Chemie

    Albright and Wilson Henkel Rhodia

    BASF Hoechst Shell Chemicals

    Dr Th.Bohme Huels Unger Fabrikker

    Condea ICI Surfactants Union Carbide

    Elf-Atochem Kao Corporation Zschimmer & Schwarz

    Table 1. Breakdown of questionnaires by study

    Surfactant Datasets Totals

    category Acute oral Skin irritation Eye irritation

    Non-ionics 109 94 102 305

    Anionics 45 31 40 116

    Totals 154 125 142 421

     2 ECETOC = European Centre for Ecotoxicology and Toxicology of Chemicals

    3

    From chemical descriptions provided, several new anionic surfactant classes were identified, extending the coverage of sub-categories 4, 5 and 11. Data were not available for sub-categories 10 and 16 (anionics), 2.1 or 4.2 (non-ionics) in this or the previous review so the TF has deleted from the tables and renumbered categories as appropriate.

    Acute oral LD50

    Anionics

    No changes to current recommendations are proposed. alkylnaphthalene sulphonates (sub-category 16) and certain of the alkyl sulphates (sub-category 2), alkylaryl sulphonate salts (sub-category 6) and fluorine surfactants (sub-category 14) are correctly classified as “harmful

    if swallowed” (R 22). New animal study data on alkyl sulphates and alkylaryl sulphonate salts are consistent with this recommendation. New data were not available on alkylnaphthalene sulphonates or fluorine surfactants.

    Non-ionics

    No changes to current recommendations are proposed. fluorine surfactants (sub-category 11) and certain of the ethoxylated fatty alcohols (sub-category 1) and ethoxylated alkylphenols (sub-category 3) are correctly classified as “harmful if swallowed” (R 22). New animal data on ethoxylated fatty alcohols and ethoxylated alkylphenols are consistent with this recommendation. New data were not available for sub-category 11.

    Skin Irritation

    Anionics

    In the absence of new data, the TF recommends no change to existing recommendations. This applies to the majority of the anionic surfactants.

    New experimental data generally support existing classification and labelling guidance. For sub-category 5 (olefin sulphonates), new skin irritation data were available on materials with an active matter concentration >80 %, at which concentration they were irritant (Xi, R 38). New data were not available on olefin sulphonates at 40-80 %, but, because in the previous review they were also found to be irritant (Xi, R 38) at 40 %, this TF recommends the same classification. Based on new data, the cocoamphodiacetates (amphoterics, sub-category 16) need not be considered irritant.

    Non-ionics

    In general, classification and labelling recommendations derived from the new animal data are consistent with existing ones.

    For three sub-categories, however, new animal data (table 2) strongly support a change from “irritating to skin” (R 38) to “not classified”, due mainly to the increasing availability of studies using a 4 hour skin exposure period, as in the OECD/EC test protocol, rather than 24 hours used in the conventional “Draize” test.

    Table 2. Non-ionics: Revised recommendations for skin irritation

     Carbon Classification

    Sub-category EO chain Conc. Existing Proposed

    length %

    1. Fatty alcohol +EO 2-5 8-18 100 R 38 NC

     >5-15 8-18 100 R 38 NC

    3. Alkylphenol+EO >7-11 8-12 100 R 38 NC

    4

    Eye Irritation

    Anionics

    Except for a few anionics (see table 3), the animal findings reviewed by the previous TF are supported by new animal study data.

    Table 3. Anionics: Recommended changes in classification due to new or expected findings

     Carbon Classification - eye

    Sub-category Cation chain Conc. Existing Proposed

    length %

    1.1 Alkylpolyglycolether H 9-14 R 36 R 41 90 carboxylic acid, 4-11 EO,

    CM degree = 80 %

    5. Olefin sulphonates Na salt 14-16 40 R 36 NC

    6. Alkylaryl sulphonate Ca salt 10-13 95 R 36 R 41 #

    salts

    8. Sulphosuccinates, di-Na salt i-10 65 R 36 R 41

    alkyl

    Amphoteric surfactants

    - Cocoalkylamidobetaine - 8-18 30 R 36* R 36

    - Cocoamphodiactetate - 10-18 30 R 36* R 36 #

    footnote: #: established by read-across rather than actual study data

    In addition, the TF recommends that anionics that are currently assigned R 36* (possibility of persistent effects on the eye) should be re-classified with “risk of serious damage to eyes”

    (R 41) to be consistent with the updated classification and labelling legislation (6) and recent industry guidance (7). Except for two product sub-categories (see following paragraph) the degree of irritation recorded throughout the studies was less than severe but the low level of irritation persisted until the end of the observation period. This persistence of effect, according to the updated guidance criteria, equates to “irreversible changes of the cornea and/or iris” and so requires the R 41 phrase.

    In contrast, for two anionic sub-categories (12.1, alkylphosphoric acid-mono/diester and 12.2, alkyl EO phosphate esters), the mean of the 24, 48 and 72 hour irritation scores was itself sufficiently severe enough to trigger a classification of “risk of serious damage to eyes” (R 41).

    For two of the amphoteric sub-categories (cocalkylamidobetaine and cocoamphodiacetate), several new rabbit eye irritation studies indicate that, at 30 % active matter, these materials are irritant (R 36) because the moderate level irritation seen shortly after application of the test material receded within 14 days.

    Non-ionics

    Except for a few non-ionics, the animal findings reviewed by the previous TF are supported by new animal study data. However, for others (categories 7 and some of categories 1 and 3), persistent effects (see previous section for more information) convinced the TF that a classification of R 41 rather than R 36* was correct.

    Summary and recommendations

    This document reports the findings of the third CESIO TF on the classification and labelling of major surfactants for human health effects according to EC legislation on dangerous

    5

    substances. The database available to this TF consisted of animal studies covering acute oral toxicity and skin and eye irritation of the anionic and non-ionic surfactants. Only studies that met current OECD/EC test standards were taken into account. Human experience data were inadequately documented to use in this exercise and human test data were too limited to use as a basis for an industry recommendation on classification and labelling of surfactants. For many of the surfactants, existing recommendations are unchanged, either because there were no additional data available or new data support these recommendations. For others, new data indicate that existing recommendations do not adequately reflect their acute oral toxicity or irritation potential when judged according to current legislation. For these, changes are recommended. New recommendations are shown in tables 4 and 5. For completeness, though not addressed by this TF, the existing recommendations for other surfactant categories are shown in Appendices 4 (quaternary ammonium compounds) and 5 (fatty amines and derivatives).

     Comments on the application of this document

    Within the surfactant industry there is an extensive safe history of the handling and use of surfactants during manufacture, supply and downstream applications and the purpose of this review, as with previous ones, is to provide guidance to underpin that for the future. The revised recommendations for classification and labelling in this report are derived from Annex V test methods (4), using current EC criteria for interpretation (6). As such, they are a basis for health and safety advice on individual surfactant substances and on preparations where no additional toxicity data are available.

    EC Directives on dangerous substances and preparations, however, do allow other approaches to classification and labelling:

    1. With regard to the use of alternative test methods using laboratory animals, the rabbit

    “Draize” test has been reported to over-predict eye irritancy of formulations containing

    surfactants for man (8-10). For many formulations, the rabbit low volume eye test may

    better reflect the eye irritancy hazard for man; it still may over-predict but less so than the

    “Draize” test (11-16).

    2. The classification and labelling recommendations in this report apply only to individual

    surfactants. When applying these to formulations containing surfactants it should be noted

    that “antagonism” has been reported in the open literature i.e. the overall irritation profile of

    some preparations has been reported to be less than that expected on account of the

    effects of the individual components (17-19). Such situations must be handled on a case

    by case basis.

    References

    1. Council Directive 67/548/EEC on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances. Adapted for the fifth time in Council Directive 83/467/EEC. OJ L257 1-33, September 16, 1983.

    2. Labelling of Surfactants, Part 1: Quats, Tenside Detergents 21 (1984) 5; Part 2: Fatty Amines and Derivatives, Tenside Detergents 22 (1985) 3; Part 3: Anionic and Non-ionic Surfactants, Tenside Detergents 22 (1985) 4.

    3. Organisation for Economic Co-operation and Development, OECD Guidelines for Testing of Chemicals, 1981.

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    4. Council Directive 67/548/EEC on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances. 5. Classification and labelling of Surfactants, CESIO report, October 12, 1990. 6. Council Directive 93/21/EEC, adapting to technical progress for the 18th time Council Directive 67/548/EEC on the Approximation of the Laws, Regulations and Administrative Provisions relating to the Classification, Packaging and Labelling of Dangerous Substances. OJ L110 Annex VI. 1-23, April 27, 1993.

    7. ECETOC Document No. 37. EC Classification of Eye Irritancy. December 1997. 8. Beckley JH (1965) Comparative Eye Testing: Man vs. Animal. Toxicology and Applied Pharmacology 7, 93-101

    9. Beckley JH, Russell TJ and Rubin LF (1969) Use of the Rhesus Monkey for predicting human response to eye irritation, Toxicology and Applied Pharmacology 15, 1-9 10. Lambert LA, Chambers WA, Green S, Gupta KC, Hill RN, Hurley PM, Lee CC, Lee JK, Liu PT, Lowther DK, Roberts CD, Seabaugh VM, Springer JA and Wilcox NL (1993), The use of low-volume dosing in the eye irritation test, Food and Chemical Toxicology 31, 99-103 11. Bruner LH and Kohrman KA (1993), The low volume eye test as a refinement to the Draize eye irritation test. Refinement and Reduction in Animal Testing. Edited by SM Niemi and JE Wilson. pp 81-93, Scientists Centre for Animal Welfare, Bethesda, Maryland, USA 12. Cormier EM, Hunter JE, Billhimer W, May J and Farage MA (1995) Use of clinical and consumer eye irritation data to evaluate the low-volume eye test, Journal of Toxicology & Cutaneous and Ocular Toxicology 14, 197-205

    13. Freeberg FE, Griffith JF, Bruce RD and Bay PHS (1984) Correlation of animal test methods with human experience for household products, Journal of Toxicology & Cutaneous and Ocular Toxicology 1(3), 53-64

    14. Freeberg FE, Hooker DT and Griffith JF (1986a) Correlation of animal eye test data with human experience for household products: an update, Journal of Toxicology & Cutaneous and Ocular Toxicology 5(2), 115-123

    15. Freeberg FE, Nixon GA, Reer PJ, Weaver JE, Bruce RD, Griffith JF and Sanders III, LW (1986b) Human and rabbit eye responses to chemical insult, Fundamental and Applied Toxicology 7, 626-634

    16. Griffith JF, Nixon GA, Bruce RD, Reer PJ and Bannan EA (1980) Dose-response studies with chemical irritants in the albino rabbit eye as a basis for selecting optimum testing conditions for predicting hazard to the human eye, Toxicology and Applied Pharmacology 55, 501-513

    17. Dillarstone A and Paye M (1993) Antagonism in concentrated surfactant systems, Contact Dermatitis 28, pp. 198

    18. Dominguez JG, Balaguer F, Parra JL and Pelejero CM (1981) The inhibitory effect of some amphoteric surfactants on the irritation potential of alkylsulphates. Int J Cosm Science 3, 57-68

    19. Rhein LD, Simion FA, Hill RL, Cagan RH, Mattai J and Maibach HI (1990) Human Cutaneous Response to a Mixed Surfactant System: Role of Solution Phenomena in Controlling Surfactant Irritation. Dermatologica 180, 18-23

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Table 4. Anionics

    Typical chemical ingredient Typical specification Recommended Symbol and R-phrases

     Cation Carbon Typical CURRENT PROPOSED

     Chain chemical Symbol Oral Skin Eye

    R- conc (%)

    K-salt 12-18 15 C, R34 C NC 34 1. Fatty acid salts Morpholine Oleyl 100 Xi, R36/38 Xi NC 38 36 1.1..Ether carboxylic acids.

    -Alkylpolyglycolether H 9-14 Xi, R36/38 Xi NC 38 41 90 carboxylic acid, 4-11 EO,

    (CM degree = 80 %)

    -Alkylpolyglycolether Na-salt 12-14 20 Xi, R36 Xi NC NC 36

    carboxylic acid, ; 4.5 EO,

    (CM degree 90 %)

    -Alkylpolyglycolether Na-salt 8-14 20 NC - NC NC NC

    carboxylic acid, 4.5 EO,

    (CM degree 90 %)

    Na-salt 12 >90 Xn, R22, Xn 22 38 2. Alkyl sulphates 41

    36*/38

     salts of 12-18 25-95 Xi, R36*/38 Xi NC 38 41

    Na, Mg, and i-

    NH4,TEA 13-15

     3. Alkylether sulphate-salts-

    Na-salt 9-15 70-75 Xi, R36*/38 Xi NC 38 -2-3 EO 41

    -2-3 EO Na-salt 9-15 25-28 Xi, R36/38 Xi NC 38 36

    - 7 EO Na-salt 9-15 65 Xi, R36/38 Xi NC 38 36

    - 2 EO Mg-salt 12-14 27 Xi, R36/38 Xi NC 38 36

    - 7 EO Na/Mg-12-18 27 Xi, R36 Xi NC NC 36

    salt

     4. Alkane sulphonates

    Na-salt 13-18 - NEW Xi NC 38 41 ; 70

     Na-salt 13-18 30 Xi, R36*/38 Xi NC 38 41

    Na-salt 14-16 >80 - 5. Olefin sulphonates Xi NC 38 41 NEW

    Na-salt 14-16 40-80 - NEW Xi NC 38 36

     Na-salt 14-16 40 Xi, R36/38 Xi NC 38 NC

    Ca-salt 10-13 95 Xi, R36/38 Xi NC 38 6. Alkylaryl sulphonate - salts 41

     Ca-salt 12 70 Xi, R36*/38 Xi NC 38 41

     Na-salt 9-14 Xi, R22, Xn 22 38 41 65 36*/38

     Na-salt 9-14 50-65 Xi, R36*/38 Xi NC 38 41

     TEA-salt 9-14 50 Xi, R36*/38 Xi NC 38 41

    Na-salt 16-18 60 Xi, R36/38 Xi NC 38 36 7. Fatty acid methylester

    sulphonates

     8. Sulphosuccinates

    Na-salt iso 8-10 65 Xi, R36/38 Xi NC 38 di-alkyl- 41

    mono-alkyl- Na-salt 12-14 32-40 Xi, R36* Xi NC NC 41

    - 12 30 Xi, R36* Xi NC NC 9. Fatty acid sarcosides 41

     - oleyl 60 Xi, R36*/38 Xi NC 38 41 10. Alkylisethionate salts Na-salt 8-18 100 - - - - -

    - 16-18 63 Xi, R36* Xi NC NC 41 10. Alkylmethyltaurides

     - 8-18 30 Xi, R36 Xi NC NC 36

    Na-salt 9 50 Xi, R36* Xi NC NC 11. Alkylphenol 41

    ethersulphates

    NEW NH4-salt 9 60 - Xi NC NC 41

continued

    8

Table 4. Anionics (continued)

    Typical chemical ingredient Typical specification Recommended Symbol and R-phrases

     Cation Carbon Typical CURRENT PROPOSED

     Chain chemical Symbol Oral Skin Eye

    R- conc (%)

     12. Fatty alcohol phosphoric

    acid esters,

    -Alkyl (4EO) phosphoric - 12-14 100 Xi, R38 Xi NC 38 NC

    acid -di/triesters

     - 16-20 100 Xi, R38 Xi NC 38 NC

    -Alkyl (8EO) phosphoric - oleyl 100 Xi, R38 Xi NC 38 NC

    acid -di/triesters

    12.1. Alkylphosphoric acid- acid iso-8 100 C, R34 C NC 34

    mono/diester -Octylphenol-7 EO acid 8 > 90 Xi, R36*/38 Xi NC 38 41

    mono/diester

    -Alkylphenol-7 EO-Na-salt 8-9 100 Xi, R36/38 Xi NC 38 36

    mono/diester

    -Phosphoric acid-K-Salt 12-14 75 Xi, R36*/38 Xi NC 38 41

    mono/diester

    12.2. Alkyl EO phosphate H 13-18 100 - Xi NC 38 41

    esters

    NEW

    Mg-salt 8-18 30 Xi, R36* Xi NC NC 13. Fatty alkanolamide 41

    TEA-salt 8-18 40 NC - NC NC NC -ether sulphates

    - 6-12 80 Xn, R22 Xn 22 NC NC 14. Fluorine surfactants

     Na-salt 8-14 30 NC * - NC NC NC

    Na-salt castor 45-80 Xi, R36*/38 Xi NC 38 15. Fatty ester sulphates 41

    oil

     Na-salt - <40 - - - - -

    Na-salt dibutyl 77 Xn, R22, 36 Xn 22 NC 36 16. Alkylnaphthalene

    sulphonate

     Amphoterics

    - 8-18 30 Xi, R36* Xi NC NC 36 -Cocoalkylamidobetaine

    -Cocoamphodiacetate - 8-18 30 Xi, R36*/38 Xi NC NC 36 -Cocoaminobetaine - 10-18 30 Xi, R36*/38 Xi NC 38 41

Footnotes: - shading indicates that no new data were available for review.

    - recommended changes are highlighted

    *: Xi, R37 - irritant by inhalation.

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Table 5: Non-ionics

    Typical chemical ingredient Typical specification Recommended Symbol and R-phrases

     Carbon Typical

     chain R- Mole - Mole- chemical CURRENT PROPOSED

     R- EO PO conc (%) Symbol Oral Skin Eye

    8-18 2-5 - 100 Xi, R36*/38 Xi NC 1. Fatty alcohol +EO NC 41

     8-18 >5-15 - 100 Xn, R22, Xn 22 NC 41

    36*/38

     8-18 >15-20 - 100 Xn, R22, 36* Xn 22 NC 41

     8-18 >20 - 100 NC - NC NC NC

    10-15 3-9 4-6 100 NC - NC NC NC 2. Fatty alcohol +EO+PO

    2.1. Fatty alcohol +PO+EO 10-14 6-6.4 1.2-8 100 - - - - -

    8-12 1-7 - 100 Xi, R36/38 Xi NC 38 36 3. Alkylphenol+EO

     8-12 >7-11 - 100 Xn, R22, Xn 22 NC 41

    36*/38

     8-12 >11-14 - 100 Xi, R36* Xi NC NC 41

     8-12 >14 - 100 NC - NC NC NC

    12-18 2-30 - 100 NC - NC NC NC 4. Fatty acid+EO

    4.1. Di-ester PEG 10-18 - 100 NC - NC NC NC 4.2 Fatty acid+PO 14-18 - 1 100 - - - - -

     44 2 100 NC - NC NC NC 5. Fatty acid+EO+PO

    12-18 2-30 - 100 NC - NC NC NC 6. Fatty acid glycerol

    ester+EO

     7. Alkylamide

    - monoethanolamide 8-18 - - 100 Xi R36* Xi NC NC 41

    - Diethanolamide - - - 100 Xi, R36*/38 Xi NC 38 41

    8-18 5 - 100 Xi, R36* Xi NC NC 7.1. Fatty acid amide+EO 41

    - 10-50 10-50 100 NC - NC NC NC 8. EO-PO block polymers

    12 20 - 100 NC - NC NC NC 9. Sorbitan fatty acid ester

     10. Others

    12-18 5-7.3 - 100 Xi, R38 Xi NC 38 NC -Fatty alcohol

     ethoxylated-n-butylether

     11. Fluorine surfactants

    12-14 - Xn, R22 Xn 22 NC NC -Ethoxylated 90 -

    perfluoroalkyl ethanol

    Footnotes: - shading indicates that no new data were available for review.

    - recommended changes are highlighted

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