Screening Assessment - Appendices

Aromatic Azo and Benzidine-based Substance Grouping
Certain Benzidine-based Dyes and Related Substances

Environment Canada
Health Canada
November 2014

Table of Contents

Appendix A: Supplementary Data Tables

Table A-1. Substance identities for individual Benzidine-based Acid Dyes
CAS RN Chemical structure Chemical formula (molecular weight in g/mol)
3701-40-4  Chemical structure of CAS RN 3701-40-4 C34H24N4O8S2Na2
(726.69)
6358-57-2 Chemical structure of CAS RN 6358-57-2 C37H30N4O10S3, 2Na
(830.82)
6459-94-5  Chemical structure of CAS RN 6459-94-5 C37h38N4O10S3, 2Na
(830.82)
6470-20-8  Chemical structure of CAS RN 6470-20-8 C32H22N6O8S2Na2
(728.67)
6548-30-7  Chemical structure of CAS RN 6548-30-7 C37h38N4012S3Na2
(862.81)
68318-35-4  Chemical structure of CAS RN 68318-35-4 C36H26N7012S3Na3
(913.80)
68400-36-2  Chemical structure of CAS RN 68400-36-2 C36H26N8O10S2Na2
(840.75)
83221-63-0  Chemical structure of CAS RN 83221-63-0 C34H26N9O13S4Na
(919.87)
89923-60-4  Chemical structure of CASRN 89923-60-4 C34H26Cl2N8O8S2Na2
(855.64)
10169-02-5  Chemical structure of CAS RN 10169-02-5 C32H20N4O8S2Na2
(698.64)
Table A-2. Substance identities for individual Benzidine-based Direct Dyes
CAS RN Chemical structure Chemical formula (molecular weight in g/mol)
72-57-1  Chemical structure of CAS RN 72-57-1 C34N6O14S4Na4
(960.80)
573-58-0  Chemical structure of CAS RN 573-58-0 C32H22N6O6S2Na2
(696.67)
992-59-6  Chemical structure of CAS RN 992-59-6 C34H26N6O6S2Na2
(724.72)
1937-37-7  Chemical structure of CAS RN 1937-37-7 C34H27N9O7S2
(737.77)
2150-54-1  Chemical structure of CAS RN 2150-54-1 C34H22N4O8S2Na4
(770.65)
2429-71-2  Chemical structure of CAS RN 2429-71-2 C34N4O9S2Na2
(742.69)
2429-74-5  Chemical structure of CAS RN 2429-74-5 C34h38N5O10S2Na4
(922.75)
6420-06-0  Chemical structure of CAS RN 6420-06-0 C34N4O8S2Na2
(726.69)
6420-22-0  Chemical structure of CAS RN 6420-22-0 C34H25N6O11S3Na3
(858.76)
6449-35-0  Chemical structure of CAS RN 6449-35-0 C34H25N5O10S2Na2
(773.70)
6548-29-4  Chemical structure of CAS RN 6548-29-4 C32H20CL2N6O6S2Na2
(765.56)
6655-95-4  Chemical structure of CAS RN 6655-95-4 C50H36N6O16S2Na4
(1132.95)
67923-89-1  Chemical structure of CAS RN 67923-89-1 C34N5O13S3Li3
(827.60)
70210-28-5  Chemical structure of CAS RN 70210-28-5 C38h38N10O9SNa2
(846.75)
71215-83-3  Chemical structure of CAS RN 71215-83-3 C29h27Cl2N5O7SNa2
(696.43)
71550-22-6  Chemical structure of CAS RN 71550-22-6 C34N6O16S4Li4
(928.60)
72252-59-6  Chemical structure of CAS RN 72252-59-6 C47H31N9O16S2Na4
(1133.90)
75659-72-2  Chemical structure of CAS RN 75659-72-2 C34N6O16S4Na3Li
(976.75)
75659-73-3  Chemical structure of CAS RN 75659-73-3 C34N6O16S4Na2Li2
(960.70)
75673-18-6  Chemical structure of CAS RN 75673-18-6 C34H25N5O13S3Na2
(860.76)
75673-19-7  Chemical structure of CAS RN 75673-19-7 C34H26N5O13S3Na
(831.78)
75673-34-6  Chemical structure of CAS RN 75673-34-6 C34N4O10S2Li2
(726.59)
75673-35-7  Chemical structure of CAS RN 75673-35-7 C34N4O10S2NaLi
(742.64)
75752-17-9  Chemical structure of CAS RN 75752-17-9 C34N6O16S4NaLi3
(944.65)
16071-86-6  Chemical structure of CAS RN 16071-86-6 C31h28N6O9SNa2Cu
(760.11)
 Table A-3. Substance identities for the Benzidine-based Cationic Indicators
CAS RN Chemical structure Chemical formula (molecular weight in g/mol)
298-83-9  Chemical structure of CAS RN 298-83-9 C40H30Cl2N10O6
(817.65)
1871-22-3  Chemical structure of CAS RN 1871-22-3 C40H30N8O2Cl2
(654.74)
Table A-4. Experimental physical and chemical properties for individual Benzidine-based Acid Dyes (with data) including substances used for read-across
CAS RN Property Value Reference
Acid Red 111 Physical state Red Powder (formulation of Lanasyn Scarlet F-3GL 103) Study Submission 2007
Acid Red 111 Melting point (°C) 170–190 (formulation of Lanasyn Scarlet F-3GL 103) Study Submission 2007
Acid Red 111 Density (kg/m3) 390 Study Submission 2007
Acid Red 111 Water solubility (mg/L) 65 000 SMS Technology Co., Ltd. 2012
Acid Red 111 Water solubility (mg/L) 25 000 (at 80°C) Study Submission 2007
Acid Red 114 Melting point (°C) 185 MITI 1992
Acid Red 114 Water solubility (mg/L) greater than 500 MITI 1992
Acid Yellow 23 (read-across for log Kow) Melting point (°C) greater than 300 Acros Organics 2006
Acid Yellow 23 (read-across for log Kow) Water solubility
(mg/L)
200 000 Marmion 1991
Acid Yellow 23 (read-across for log Kow) Water solubility
(mg/L)
300 000 Green 1990
Acid Yellow 23 (read-across for log Kow) Water solubility
(mg/L)
greater than 2% MITI 1992
Acid Yellow 23 (read-across for log Kow) Log Kow −0.017 CITI 1992
Acid Yellow 36 (read-across for log Kow) Water solubility Soluble Ricca Chemical Co. 2008; Acros Organics 2009a
Acid Yellow 36 (read-across for log Kow) Log Kow 0.7 Tonogai et al. 1982
Acid Orange 7
(read-across for log Kow)
Melting point (°C) 164 Acros Organics 2009b
Acid Orange 7
(read-across for log Kow)
Log Kow 0.57 Tonogai et al. 1982
Acid Orange 7
(read-across for log Kow)
Water solubility
(mg/L)
116 000 Acros Organics 2009b
Acid Orange 7
(read-across for log Kow)
Water solubility
(mg/L)
50 000 Merck Index 1989
Table A-5. Experimental physical and chemical properties for individual Benzidine-based Direct Dyes (with data)
CAS RN Property Value Reference
Direct Blue 14 Physical state Bluish-grey powdered solid ChemicalBook 2008a
Direct Blue 14 Melting point (°C) greater than 300 (decomposes) ChemicalBook 2008a
Direct Blue 14 Melting point (°C) greater than 300 (decomposes) CHRIP ©2002-2012
Direct Blue 14 Melting point (°C) 300 Øllgaard et al. 1998
Direct Blue 14 Water solubility (mg/L) 20 000 CHRIP ©2002-2012
Direct Blue 14 Water solubility (mg/L) 10 000 ChemicalBook 2008a
Direct Black 38 Melting point (°C) 109–110 ChemicalBook 2008b
Direct Black 38 Water solubility (mg/L) 93 000 Isik and Sponza 2004
Direct Red 28 Physical state Brown-red powder ChemicalBook 2008c
Direct Red 28 Melting point (°C) greater than 360  ChemicalBook 2008c; Alfa Aesar ©2011
Direct Red 28 Density (kg/m3) 995 ChemicalBook 2008c
Direct Red 28 Log Kow 0.77 Tonogai et al. 1982
Direct Red 28 Water solubility (mg/L) 116 000 Dehn 1917
Direct Brown 95 Physical state Dark brown microcrystals or charcoal black powder ChemicalBook 2008d
Direct Blue 15 Physical state Deep purple to dark blue microcrystalline powder ChemicalBook 2008e
Direct Blue 15 Water solubility (mg/L) 30 000 Brown 1992
Direct Red 2 Melting point (°C) ~290 (decomposes) Chemexper 2012
Direct Blue 8 Physical state Bluish-black powder ChemicalBook 2008f
Direct Violet 28 Physical state Bluish-black powder ChemicalBook 2008g
Direct Blue 151 Physical state Bluish-black powder ChemicalBook 2008h
Table A-6. Physical and chemical properties for the Cationic Indicators subgroup
CAS RN Property Value Reference
TDBD Physical state Yellow crystalline solid ChemicalBook 2008i
TDBD Melting point (°C) 255 ChemicalBook 2008i
TDBD Melting point (°C) ~190 Alfa Aesar ©2011
TDBD Water solubility (mg/L) 9000 Green 1990
TDBPD Physical state Yellow crystals ChemicalBook 2008j
TDBPD Melting point (°C) 189 Sigma-Aldrich 2012a
TDBPD Melting point (°C) 200 Chemical Book 2008j
TDBPD Water solubility (mg/L) 10 000 Green 1990
Basic Dyes Log Kow Low Øllgaard et al. 1998
Table A-7. Estimated physical and chemical properties for the Benzidine-based Precursors subgroup
CAS RN Property Value Reference
Naphthol AS-BR Melting point (°C) 246 MPBPWIN 2010
Naphthol AS-BR Melting point (°C) 350 MPBPWIN 2010
Naphthol AS-BR Boiling point (ºC) 927.49 MPBPWIN 2010
Naphthol AS-BR Vapour pressure (Pa) 7.7 × 10−25 MPBPWIN 2010
Naphthol AS-BR Henry’s Law constant (Pa·m3/mol) 1.96 × 10−15 HENRYWIN 2011
Naphthol AS-BR Log Kow 7.75 KOWWIN 2010
Naphthol AS-BR Log Koc 1.43 × 105 (MCI method) KOCWIN 2010
Naphthol AS-BR Log Koc 8.27 × 105 (Kow method)
Naphthol AS-BR Log Koa 25.853 KOAWIN 2010
Naphthol AS-BR Water solubility (mg/L) 8.97 × 10−6 WSKOWWIN 2010
Naphthol AS-BR Water solubility (mg/L) 1.44 × 10−5 WATERNT 2010
TCDB Melting point (°C) 250.21 MPBPWIN 2010
TCDB Boiling point (ºC) 580.51 MPBPWIN 2010
TCDB Vapour pressure (Pa) 1.12 × 10−10 MPBPWIN 2010
TCDB Henry’s Law constant (Pa·m3/mol) 5.81 × 10−9 HENRYWIN 2011
TCDB Log Kow 5.13 KOWWIN 2010
TCDB Log Koc 2.2 (MCI method) KOCWIN 2010
TCDB Log Koc 5.47 (Kow method)
TCDB Log Koa 16.760 KOAWIN 2010
TCDB Water solubility (mg/L) 0.2588 WSKOWWIN 2010
TCDB Water solubility (mg/L) 32.801 WATERNT 2010
Table A-8. Physical and chemical properties for the Benzidine Derivatives subgroup
Chemical Property Value or range Reference
3,3′-DMB Physical state Light brown powder Sigma-Aldrich 2012b
3,3′-DMB Melting point (°C) 128–132 Alfa Aesar ©2011
3,3′-DMB Melting point (°C) 131.5 PhysProp 2006
3,3′-DMB Melting point (°C) 129–131 Merck Index 2006
3,3′-DMB Melting point (°C) 147.85 MPBPWIN 2010
3,3′-DMB Boiling point (ºC) 200 ACGIH 1986
3,3′-DMB Boiling point (ºC) 339 PhysProp 2006
3,3′-DMB Boiling point (ºC) 300 Hawley 1981
3,3′-DMB Boiling point (ºC) 393.08 MPBPVPWIN 2010
3,3′-DMB Density (kg/m3) 1234 ICSC 1998
3,3′-DMB Vapour pressure
(Pa)
9.23 × 10−5
(6.92 × 10−7 mmHg)
Neely and Blau 1985
3,3′-DMB Vapour pressure
(Pa)
2.74 × 10−2
(2.06 × 10−5 mmHg)
MPBPWIN 2010
3,3′-DMB Henry’s Law constant
(Pa·m3/mol)
6.38 × 10−6
(Bond estimation method)
8.21 × 10−6
(Group contribution method)
HENRYWIN 2011
3,3′-DMB Henry’s Law constant 6.37 × 10−7
(6.29 × 10−11 atm·m3/mol)
Meylan and Howard 1991
3,3′-DMB (Pa·m3/mol) 2.59 × 10−2
(2.56 × 10−7 atm·m3/mol)
(EVA method)Footnote Appendix A Table A8 [a]
HENRYWIN 2011
3,3′-DMB Log Kow 2.34 Hansch et al. 1995
3,3′-DMB Log Kow 2.39 MITI 1992
3,3′-DMB Log Kow 3.02 KOWWIN 2010
3,3′-DMB Log Kow 2.43 (EVA method)Footnote Appendix A Table A8 [b] KOWWIN 2010
3,3′-DMB Log Koc 2.17 (from log Kow)
3.50 (from MCI)
KOCWIN 2010
3,3′-DMB Log Koa 10.93 KOAWIN 2010
3,3′-DMB Water solubility
(mg/L)
50 MITI 1992
3,3′-DMB Water solubility (mg/L) 1300 Bowman et al. 1976
3,3′-DMB Water solubility (mg/L) 27.1 WATERNT 2010
3,3′-DMB Water solubility (mg/L) 134 MPBPWIN 2010
3,3′-DMB Water solubility (mg/L) 51.263 (EVA method)Footnote Appendix A Table A8 [c] WATERNT 2010
3,3′-DMB pKa 4.6 Kawakami et al. 2010
3,3′-DMB pKa pKa1 = 4.5
pKa2 = 3.4–3.5
Perrin 1965
3,3′-DMB pKa pKa1 = 3.3 Kubota and Ezumi 1980
3,3′-DMB·2HCl Physical state Light red powder Sigma Aldrich 2012c
3,3′-DMB·2HCl Melting point (°C) 340 Sigma Aldrich 2012c
3,3′-DMB·2HCl Melting point (°C) 210 Beilstein 1984
3,3′-DMB·2HCl Water solubility (mg/L) Soluble in water CHRIP ©2002-2012
3,3′-DMB·2HCl Water solubility (mg/L) 10 000 – 50 000 ChemBioFinder ©1998–2013
3,3′-DMOB Physical state Beige brown crystalline powder Acros Organics 2007
3,3′-DMOB Melting point (°C) 137 Lewis 1997
3,3′-DMOB Melting point (°C) 136–137 Alfa Aesar ©2011
3,3′-DMOB Melting point (°C) 137–138 Merck Index 2006
3,3′-DMOB Melting point (°C) 161.6 MPBPWIN 2010
3,3′-DMOB Boiling point (°C) 356 SRC 2011
3,3′-DMOB Boiling point (°C) 417.2 MPBPWIN 2010
3,3′-DMOB Vapour pressure
(Pa)
9.45 × 10−4
(7.09 × 10−6 mmHg)
MPBPWIN 2010
3,3′-DMOB Vapour pressure
(Pa)
1.66 × 10−5
(1.25 × 10−7 mmHg)
Neely and Blau 1985
3,3′-DMOB Henry’s Law constant
(Pa·m3/mol)
1.83 × 10−8
(1.81 × 10−13 atm·m3/mol)
(Bond estimation method)
4.72 × 10−6
(4.66 × 10−11 atm·m3/mol)
(Group contribution method)
HENRYWIN 2011
3,3′-DMOB Henry’s Law constant
(Pa·m3/mol)
4.762 × 10−6
(4.7 × 10−11 atm·m3/mol)
Meylan and Howard 1991
3,3′-DMOB Henry’s Law constant
(Pa·m3/mol)
7.45 × 10−5
(7.35 × 10−10 atm·m3/mol) (EVA method)[a]
HENRYWIN 2011
3,3′-DMOB Log Kow 1.81 Debnath and Hansch 1992
3,3′-DMOB Log Kow 2.08 KOWWIN 2010
3,3′-DMOB Log Kow 1.5 (EVA method)Footnote Appendix A Table A8 [d] KOWWIN 2010
3,3′-DMOB Log Koc 1.99 (from log Kow)
2.71 (from MCI)
KOCWIN 2010
3,3′-DMOB Log Koa 13.211 KOAWIN 2010
3,3′-DMOB Water solubility (mg/L) 60 mg/L at 25°C Bowman et al. 1976
3,3′-DMOB Water solubility (mg/L) Insoluble NIOSH 2012
3,3′-DMOB Water solubility (mg/L) Slightly soluble Chemical Book 2008k
3,3′-DMOB Water solubility (mg/L) 77.54 WATERNT 2010
3,3′-DMOB Water solubility (mg/L) 146.8 (EVA method)e WATERNT 2010
3,3′-DMOB Water solubility (mg/L) 351 WSKOWWIN 2010
3,3′-DMOB pKa 4.7 Kawakami et al. 2010
3,3′-DMOB pKa 4.2 (estimated) PhysProp 2006
TODI Physical state Colourless to pale yellow flakes Sigma-Aldrich 2012d
TODI Melting point (°C) 70–72 Chemical Book 2008l
TODI Melting point (°C) 70 Woolrich 1973
TODI Melting point (°C) 71 PhysProp 2006
TODI Melting point (°C) 71.7 ECHA 2012
TODI Melting point (°C) 115.98 MPBPWIN 2010
TODI Boiling point
(°C)
371–373 ECHA 2012
TODI Boiling point 314 Kirk-Othmer 1981
TODI (°C) 364.35 MPBPVPWIN 2010
TODI Density (kg/m3) 1330 ECHA 2012
TODI Density (kg/m3) 1156 (at 80°C) Kirk-Othmer 1981
TODI Vapour pressure
(Pa)
2.95 × 10−3
(2.21 × 10−5 mmHg)
MPBPWIN 2010
TODI Henry’s Law constant
(Pa·m3/mol)
NA NA
TODI Log Kow NA NA
TODI Log Koc NA NA
TODI Log Koa 10.466 KOAWIN 2010
TODI Water solubility (mg/L) NA NA
TODI pKa Not applicable Not applicable
4N-TMB Physical state Tan-coloured powder Acros Organics 2008
4N-TMB Melting point (°C) 193–195 Acros Organics 2008
4N-TMB Melting point (°C) 193 ChemSpider ©2011
4N-TMB Melting point (°C) 194 SRC 2011
4N-TMB Melting point (°C) 108.5 MPBPWIN 2010
4N-TMB Boiling point
(°C)
353.7 MPBPWIN 2010
4N-TMB Vapour pressure
(Pa)
2.17 × 10−3
(1.63 × 10−5 mmHg)
Neely and Blau 1985
4N-TMB Vapour pressure
(Pa)
2.41 × 10−4
(1.08 × 10−7 mmHg)
MPBPWIN 2010
4N-TMB Henry’s Law constant
(Pa·m3/mol)
1.06 × 10−2
(Bond estimation method)
(1.05 × 10−7 atm·m3/mol)
HENRYWIN 2011
4N-TMB Henry’s Law constant
(Pa·m3/mol)
4.94 × 10−1
(4.88 × 10−6 atm·m3/mol)
(EVA method)[a]
HENRYWIN 2011
4N-TMB Log Kow 4.11 KOWWIN 2010
4N-TMB Log Kow 3.53 (EVA method)[b] KOWWIN 2010
4N-TMB Log Koc 3.17 (from MCI)
3.07 (from log Kow)
2.75 (from corrected log Kow)
KOCWIN 2010
4N-TMB Log Koa 9.48 KOAWIN 2010
4N-TMB Water solubility (mg/L) 8.23 Meylan et al. 1996
4N-TMB Water solubility (mg/L) 0.65 WSKOWWIN 2010
4N-TMB Water solubility (mg/L) 25.85 (EVA method)[d] WSKOWWIN 2010
4N-TMB Water solubility (mg/L) 17.87 WATERNT 2010
4N-TMB Water solubility (mg/L) 33.833 (EVA method)[c] WATERNT 2010
Table A-9a. Summary of modelled data for degradation of Benzidine-based Acid DyesFootnote Appendix A Table A9a [a]
Fate process Model and model basis Model result and prediction Extrapolated half-life (days)
Atmospheric oxidation (air) AOPWIN 2010Footnote Appendix A Table A9a [b]  t½ = 0.05–1.38 days less than or equal to 2
Ozone reaction (air) AOPWIN 2010[b] N/AFootnote Appendix A Table A9a [c] N/A
Hydrolysis (water) HYDROWIN 2010[b] Not in training set N/A
Primary degradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 4: Expert Survey
(qualitative results)
2.15–2.92Footnote Appendix A Table A9a [d]
(biodegrades slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 3: Expert Survey
(qualitative results)
0.48–1.55[d]
(biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 5:
MITI linear probability
−2.29 to −1.01Footnote Appendix A Table A9a [e]
(biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 6:
MITI non-linear probability
0[e]
 (biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) DS TOPKAT c2005–2009
Probability
N/A  
Ultimate biodegradation: Biodegradation (aerobic) (water) CATALOGIC ©2004–2011
% BOD

% BOD = 0–20

(biodegrades slowly)

greater than or equal to 182
Table A-9b. Summary of modelled data for degradation of Benzidine-based Direct DyesFootnote Appendix A Table A9b [a]
Fate process Model and model basis Model result and prediction Extrapolated half-life (days)
Atmospheric oxidation (air) AOPWIN 2010Footnote Appendix A Table A9b [b]  t½ = 0.21–0.71 days less than or equal to 2
Ozone reaction (air) AOPWIN 2010[b] N/AFootnote Appendix A Table A9b [c] N/A
Hydrolysis (water) HYDROWIN 2010[b] N/A, not in training set N/A
Primary biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 4: Expert Survey
(qualitative results)
2.29–3.2Footnote Appendix A Table A9b [d]
(biodegrades slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 3: Expert Survey
(qualitative results)
0.37–1.37[d]
 (biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 5:
MITI linear probability
−2.01 to −0.79Footnote Appendix A Table A9b [e]
(biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 6:
MITI non-linear probability
0[e]
 (biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) DS TOPKAT c2005–2009
Probability
N/A  
Ultimate biodegradation: Biodegradation (aerobic) (water) CATALOGIC  ©2004–2011
% BOD
% BOD = 0–8
(biodegrades very slowly)
greater than or equal to 182
Table A-9c. Summary of modelled data for degradation of Benzidine-based Cationic IndicatorsFootnote Appendix A Table A9c [a]
Fate process Model and model basis Model result and prediction Extrapolated half-life (days)
Atmospheric oxidation (air) AOPWIN 2010Footnote Appendix A Table A9c [b]  t½ = 0.143–0.16 days less than or equal to 2
Ozone reaction (air) AOPWIN 2010[b] N/AFootnote Appendix A Table A9c [c] N/A
Hydrolysis (water) HYDROWIN 2010[b] N/A, not in training set N/A
Primary biodegradation:  Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 4: Expert Survey
(qualitative results)
2.62–3.08Footnote Appendix A Table A9c [d]
(biodegrades slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 3: Expert Survey
(qualitative results)
0.98–1.72[d]
(biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 5:
MITI linear probability
−1.51 to −0.63Footnote Appendix A Table A9c [e]
(biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 6:
MITI non-linear probability
0[e]
 (biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) DS TOPKAT c2005–2009 Probability N/A  
Ultimate biodegradation: Biodegradation (aerobic) (water) CATALOGIC ©2004–2011
% BOD
% BOD =7
(biodegrades very slowly)
greater than or equal to 182
Table A-9d. Summary of modelled data for degradation of Benzidine-based PrecursorsFootnote Appendix A Table A9d [a]
Fate process Model and model basis Model result and prediction Extrapolated half-life (days)
Atmospheric oxidation (air) AOPWIN 2010Footnote Appendix A Table A9d [b]  t½ = 0.08–0.09 days less than or equal to 2
Ozone reaction (air) AOPWIN 2010[b] N/AFootnote Appendix A Table A9d [c] N/A
Hydrolysis (water) HYDROWIN 2010[b] N/A, not in training set N/A
Primary biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 4: Expert Survey
(qualitative results)
3.50–3.65Footnote Appendix A Table A9d [d]
(may biodegrade fast)
less than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 3: Expert Survey
(qualitative results)
1.80–2.31[d]
(biodegrades slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 5:
MITI linear probability
−0.11 to 0.11Footnote Appendix A Table A9d [e]
(biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[b]
Submodel 6:
MITI non-linear probability
0–0.01[e]
 (biodegrades very slowly)
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) DS TOPKAT c2005–2009 Probability NA  
Ultimate biodegradation: Biodegradation (aerobic) (water) CATALOGIC ©2004–2011
% BOD
% BOD = 7–26
(biodegrades slowly)
greater than or equal to 182
Table A-9e. Summary of calculated and modelled data for degradation of Benzidine DerivativesFootnote Appendix A Table A9e [a]
Fate process Model and model basis Model result and prediction Extrapolated half-life (days)
Atmospheric oxidation (air) Meylan and Howard 1993Footnote Appendix A Table A9e [b]
(calculated)
t½ = 0.167–0.25 day
(1.3 × 10−10 to 1.9 × 10−10
cm3 molecule – sec)
less than or equal to 2
Atmospheric oxidation (air) AOPWIN 2010Footnote Appendix A Table A9e [c]  t½ = 0.052–0.079 day less than or equal to 2
Ozone reaction (air) AOPWIN 2010[c] N/AFootnote Appendix A Table A9e [d] N/A
Hydrolysis (water)
(CAS RN 91-97-4)
HYDROWIN 2010[c] t½ = less than 10 days (even at low pHs) N/A
Primary biodegradation:  Biodegradation (aerobic) (water) BIOWIN 2008[c]
Submodel 4: Expert Survey
(qualitative results)
2.925–3.433Footnote Appendix A Table A9e [e]
 “may biodegrade fast”
less than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[c]
Submodel 3: Expert Survey
(qualitative results)
2.158–2.31[e]
 “biodegrades slowly”
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[c]
Submodel 5:
MITI linear probability
−0.105 to 0.111Footnote Appendix A Table A9e [f]
 “biodegrades very slowly”
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) BIOWIN 2008[c]
Submodel 6:
MITI non-linear probability
0.006–0.027[f]
 “biodegrades very slowly”
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) DS TOPKAT c2005–2009 
Probability
0–0.3[f]
“biodegrades slowly”
greater than or equal to 182
Ultimate biodegradation: Biodegradation (aerobic) (water) CATALOGIC ©2004–2011
% BOD
% BOD = 0.6–15.85
“biodegrades slowly”
greater than or equal to 182
Table A-10. Empirical data for aquatic toxicity for substances in the Benzidine Derivatives subgroup
CAS RN Test organism Type of test (duration) Endpoint Value (mg/L)b Reference
91-97-4 Rainbow trout
Oncorhynchus mykiss
Acute (96 h) NOEC 0.18–0.19 ECHA 2012
91-97-4 Rainbow trout
Oncorhynchus mykiss
Acute (96 h) LC50 0.25 ECHA 2012
119-93-7 Alga
Pseudokircheneriella subcapitata
Chronic (72 h) NOEC (growth area under the curve) 0.32 MITI 2000
119-93-7 Alga Chronic (72 h) NOEC (growth rate) 0.45 MITI 2000
119-93-7 Pseudokircheneriella subcapitata Chronic (72 h) EC50 (growth area under the curve) 2 MITI 2000
119-93-7 Alga Chronic (72 h) EC50 (growth rate) 6.3 MITI 2000
119-93-7 Daphnia Chronic (21 days) NOEC
(reproduction)
0.16 Kuhn et al. 1989
119-93-7 Daphnia Acute (24 h) EC0 (behaviour) 1.5 Kuhn 1989
119-93-7 Daphnia Acute (24 h) EC50 (behaviour) 3.2 Kuhn 1989
119-93-7 Daphnia Chronic (21 days) NOEC 0.26 MITI 2000
119-93-7 Daphnia Chronic (21 days) EC50 0.64 MITI 2000
119-93-7 Daphnia Acute (48 h) EC50
(immobilization)
4.5 MITI 2000
119-93-7 Fish
Oryzias latipes
Acute (96 h) LC50 13 MITI 2000
119-93-7 Fish
Oryzias latipes
Acute (48 h) LC50 55.8 MITI 1992
119-93-7 Green alga
Desmodesmus subspicatus
Chronic (72 h)
(growth rate)
NOEC greater than or equal to 1.5 ECHA 2012
119-93-7 Green alga
Desmodesmus subspicatus
Chronic (72 h)
(growth rate)
EC50 greater than 1.5 ECHA 2012
119-93-7 Daphnia magna Chronic (48 h) NOEC greater than or equal to 1.2 ECHA 2012
119-93-7 Daphnia magna Chronic (48 h) EC50 greater than 1.2 ECHA 2012

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Appendix B: Aquatic PEC Calculations for Benzidine-based Acid and Direct Dyes Used in Textile Dyeing

The method used for the stepwise estimation of the aquatic PECs from the textile wet processing sector is described as follows.

Step 1: Maximum annual quantity of the Benzidine-based Acid or Direct Dyes used by the textile wet processing sector

There are 10 acid dyes in the Benzidine-based Acid Dyes group. Survey data showed that one acid dye was reported in an annual quantity of 100–1000 kg/year, and no quantities were reported for each of the remaining nine acid dyes with the reporting threshold of 100 kg/year. The maximum annual quantity of the Benzidine-based Acid Dyes would then be 1900 kg/year by adding together the upper end of one reported quantity (1000 kg/year) and 9 times the 100 kg/year threshold.

Maximum annual quantity of Benzidine-based Acid Dyes used by the textile sector = 1900 kg/year

There are 25 direct dyes in the Benzidine-based Direct Dyes group. Survey data showed that one direct dye was reported in an annual quantity of 0–100 kg/year, and no report was received for each of the remaining 24 direct dyes with the reporting threshold of 100 kg/year. The maximum annual quantity of the Benzidine-based Direct Dyes would then be 2500 kg/year by adding together the upper end of one reported quantity (100 kg/year) and 24 times the 100 kg/year threshold.

Maximum annual quantity of Benzidine-based Direct Dyes used by the textile sector = 2500 kg/year

Step 2: Maximum annual quantity of the Benzidine-based Acid or Direct Dyes used at one mill

The highest quantity of the Benzidine-based Acid Dyes sold to one single textile mill was 300 kg/year according to industry surveys conducted for the years 2005 and 2006 under Canada Gazette notices issued pursuant to section 71 of CEPA 1999 (Canada 2006b, 2008b). This highest quantity is selected as the maximum quantity of the Benzidine-based Acid Dyes used at any given single mill. No survey data are available on the highest quantity of the Benzidine-based Direct Dyes sold to one single textile mill above the 100 kg/year reporting threshold. Thus, the maximum quantity of the Benzidine-based Direct Dyes used at any given single mill is assumed to be 100 kg/year.

Maximum annual quantity of the Benzidine-based Acid Dyes used at one mill = 300 kg/year

Maximum annual quantity of the Benzidine-based Direct Dyes used at one mill = 100 kg/year

Step 3: Daily use quantity at one mill

The daily use quantity of the Benzidine-based Acid or Direct Dyes at one mill is estimated based on a typical daily quantity of textile dyed and a typical dye use rate. Typically, a dyelot is completed within 6 hours from batch dyeing or 8 hours from continuous dyeing (US EPA 1994). When a mill operates three shifts or 24 hours/day, the maximum number of dyelots completed per day would be four dyelots, as determined for batch dyeing. One dyelot typically consists of 454 kg of textile, so the daily quantity of textile dyed would be 1816 kg/day (454 kg/dyelot × 4 dyelots/day). For a typical dye use rate of 0.02 kg dyes per kilogram of textile (Cai et al. 1999), the daily quantity of the Benzidine-based Acid or Direct Dyes used at one mill is estimated as:

Daily quantity of the Benzidine-based Acid or Direct Dyes used at one mill = 1816 kg/day × 0.02 kg/kg = 36 kg/day

Step 4: Number of annual release days from one mill

The number of annual release days from one mill is assumed to be the same as the number of the annual operation days, since the wastewater resulting from dyeing (spent bath and rinse water) is generally not stored on site and is released to municipal sewers soon after it is generated. The number of annual release days is then estimated as 8.3 days for the Benzidine-based Acid Dyes and 2.8 days for the Benzidine-based Direct Dyes by dividing the maximum annual quantity (300 kg/year for the Benzidine-based Acid Dyes or 100 kg/year for the Benzidine-based Direct Dyes) used at one mill by their daily use quantity (36 kg/day). These values represent the maximum durations for the continuous release of the Benzidine-based Acid or Direct Dyes via wastewater.

Number of annual release days from one mill for the Benzidine-based Acid Dyes = 8.3 days

Number of annual release days from one mill for the Benzidine-based Direct Dyes = 2.8 days

Step 5: Daily release to sewers from one mill

The daily release of the Benzidine-based Acid or Direct Dyes to sewers is estimated based on their respective emission factors to wastewater. On average, the emission factor is 10% for acid dyes and 12% for direct dyes (OECD 2004). The daily release to sewers of the Benzidine-based Acid or Direct Dyes from one mill is then calculated by multiplying the daily use quantity by the emission factor.

Daily release of the Benzidine-based Acid Dyes to sewers from one mill = 36 kg/day × 10% = 3.6 kg/day

Daily release of the Benzidine-based Direct Dyes to sewers from one mill = 36 kg/day × 12% = 4.3 kg/day

These release estimates are based on the assumption of zero removal for on-site wastewater treatment, because specific information is not available on the type of on-site wastewater treatment at each of the mills evaluated. The use of the zero removal assumption yields conservative release estimates.

Step 6: Estimated wastewater influent concentration

The concentration of the Benzidine-based Acid or Direct Dyes in wastewater influent is calculated by dividing the daily release quantity (3.6 kg/day for the Benzidine-based Acid Dyes or 4.3 kg/day for the Benzidine-based Direct Dyes) by the wastewater flow (L/day) of a municipal wastewater treatment system. The wastewater flow varies from location to location. For example,

Wastewater flow in Arthur, ON = 1 041 600 L/day

Wastewater flow in Montréal, QC = 2 786 797 997 L/day

The concentrations of the Benzidine-based Acid or Direct Dyes in wastewater influent at these two locations are determined as:

Wastewater influent concentration for the Benzidine-based Acid Dyes in Arthur, ON

= 3.6 kg/day / 1 041 600 L/day = 3.46 × 10−6 kg/L = 3460 mg/L

Wastewater influent concentration for the Benzidine-based Acid Dyes in Montréal, QC

= 3.6 kg/day / 2 786 797 997 L/day = 1.29 × 10−9 kg/L = 1.29 mg/L

Wastewater influent concentration for the Benzidine-based Direct Dyes in Arthur, ON

= 4.3 kg/day / 1 041 600 L/day = 4.13 × 10−6 kg/L = 4130 mg/L

Wastewater influent concentration for the Benzidine-based Direct Dyes in Montréal, QC

= 4.3 kg/day / 2 786 797 997 L/day = 1.54 × 10−9 kg/L = 1.54 mg/L

Step 7: Removal by off-site wastewater treatment systems

No suitable model was available to estimate the removal of the Benzidine-based Acid or Direct Dyes through wastewater treatment systems. The models used by Environment Canada (e.g., ASTreat 2006; STP 2006) are designed for neutral substances and are not suitable for ionic chemicals. Since both Benzidine-based Acid Dyes and Benzidine-based Direct Dyes are water-soluble anionic compounds (US EPA 1996), they fall outside the domain of applicability for the above-mentioned models.

Literature data are available on the wastewater treatment removal of azo dyes in general and can be used to provide removal estimates for the Benzidine-based Acid or Direct Dyes, since they are azo dyes. In a Danish survey report (Øllgaard et al. 1998), removal rates of 40–80% were found for azo dyes. This removal range is a result of adsorption to sludge alone, without accounting for any additional removal by abiotic or biotic degradation. This range is therefore expected to occur with all three common wastewater treatment types (primary, secondary and lagoons), since all these systems provide sludge removal or settling. As an approximation, an average (60%) of this removal range is selected for the Benzidine-based Acid or Direct Dyes. The average is judged to be more statistically representative than any other value of the different wastewater treatment systems involved and the different individual azo dye substances in the Benzidine-based Acid or Direct Dyes.

Wastewater treatment removal for the Benzidine-based Acid or Direct Dyes = 60%

Step 8: Lagoon dilution

Many textile mills are located in municipalities served by lagoons. These lagoons contain large volumes of water and have long hydraulic retention times. The retention time of a lagoon is measured in weeks to months, according to field data collected through the CMP Monitoring and Surveillance Program at Environment Canada (Smyth 2012). The implication of a long retention time is that a substance entering a lagoon within a relatively short duration is subject to not only removal, but also dilution. As a result, the substance concentration in the lagoon effluent is reduced by both removal and dilution. This is the case with the release of the Benzidine-based Acid or Direct Dyes. The duration of the release within a year was estimated previously as 8.3 days for the Benzidine-based Acid Dyes or 2.8 days for the Benzidine-based Direct Dyes (see Step 4 above). These durations are short compared with a lagoon’s residence time. Dilution is therefore justified. Such dilution is, however, not expected in primary or secondary treatment systems, because their hydraulic retention times are short, typically measured in hours.

No quantitative method is available to determine the degree of lagoon dilution. Nevertheless, the ratio of a lagoon’s retention time to a substance’s release duration can be considered as the maximum dilution, because the ratio is equivalent to the full dilution or the volume ratio of the entire lagoon water to the wastewater containing a specific substance. As an estimate, the lagoon retention time in weeks to months is interpreted as 42 days (6 weeks) to 84 days (12 weeks). The full dilution is then determined to be 5- to 10-fold for the Benzidine-based Acid Dyes or 15- to 30-fold for the Benzidine-based Direct Dyes by dividing the retention time (42–84 days) by the release duration (8.3 days for the Benzidine-based Acid Dyes or 2.8 days for the Benzidine-based Direct Dyes). As an approximation, an average is selected from each range for lagoon dilution, 7.5-fold for the Benzidine-based Acid Dyes and 22.5-fold for the Benzidine-based Direct Dyes.

Lagoon dilution for the release of the Benzidine-based Acid Dyes = 7.5

Lagoon dilution for the release of the Benzidine-based Direct Dyes = 22.5

Step 9: Wastewater effluent concentration

The concentration of the Benzidine-based Acid or Direct Dyes in wastewater effluent is determined by applying the wastewater treatment removal to the influent concentration. Dilution is also considered for lagoons. For example, the wastewater from a mill in Montréal, QC, is discharged to a primary system, and only the 60% removal is used to estimate the effluent concentration.

Wastewater effluent concentration for the Benzidine-based Acid Dyes in Montréal, QC

= influent concentration × (1 − removal)

= 1.29 µg/L × (1 − 60%) = 0.52 µg/L

Wastewater effluent concentration for the Benzidine-based Direct Dyes in Montréal, QC

= influent concentration × (1 − removal)

= 1.54 µg/L × (1 − 60%) = 0.62 µg/L

For a mill in Arthur, ON, the mill wastewater is discharged to a lagoon, and the concentration of the Benzidine-based Acid or Direct dyes in the effluent is estimated as:

Wastewater effluent concentration for the Benzidine-based Acid Dyes in Arthur, ON

= influent concentration × (1 − removal) / lagoon dilution for the Benzidine-based Acid Dyes

= 3460 µg/L × (1 − 60%) / 7.5 = 185 µg/L

Wastewater effluent concentration for the Benzidine-based Direct Dyes in Arthur, ON

= influent concentration × (1 − removal) / lagoon dilution for the Benzidine-based Direct Dyes

= 4130 µg/L × (1 − 60%) / 22.5 = 73.4 µg/L

Step 10: Predicted aquatic environmental concentration

The predicted aquatic environmental concentration (aquatic PEC) is determined by applying the receiving water dilution to the effluent concentration. Since the aquatic PEC is assessed near the discharge point, the receiving water dilution selected should also be applicable to this condition. The full dilution potential of a river is considered appropriate if it is between 1 and 10. Otherwise, the dilution is kept at 10 for both large rivers and still waters.

For the wastewater treatment system (a lagoon) in Arthur, ON, the receiving water is the Conestogo River, and its dilution potential is determined to be 7.64 (ratio of the 10th percentile river flow 7 957 160 L/day to the wastewater effluent flow 1 041 600 L/day). The aquatic PEC for the Benzidine-based Acid or Direct Dyes at the site of Arthur, ON, is then estimated as:

Aquatic PEC for the Benzidine-based Acid Dyes at site of Arthur, ON

= Wastewater effluent concentration / Receiving water dilution

= 185 µg/L / 7.64 = 24.2 µg/L

Aquatic PEC for the Benzidine-based Direct Dyes at site of Arthur, ON

= Wastewater effluent concentration / Receiving water dilution

= 73.4 µg/L / 7.64 = 9.6 µg/L

For the wastewater treatment system (primary) in Montréal, QC, the receiving water, the St. Lawrence River, has a very large flow, so the dilution is limited to 10 near the discharge point. The aquatic PEC for the Benzidine-based Acid or Direct Dyes at the site of Montréal, QC, is then estimated as:

Aquatic PEC for the Benzidine-based Acid Dyes at site of Montréal, QC

= Wastewater effluent concentration / Receiving water dilution

= 0.52 µg/L / 10 = 0.052 µg/L

Aquatic PEC for the Benzidine-based Direct Dyes at site of Montréal, QC

= Wastewater effluent concentration / Receiving water dilution

= 0.62 µg/L / 10 = 0.062 µg/L

Although there are sites where multiple textile mills are identified to discharge to one single wastewater treatment system, the chance of more than one mill at any of these sites using and releasing the same acid or direct dyes is expected to be low. This is because mills are operated year-round, while the release from one single mill occurs only for 8.3 days for the Benzidine-based Acid Dyes and 2.8 days for the Benzidine-based Direct Dyes. The release overlapping within these short periods is therefore a low possibility. As a result, the aquatic PEC resulting from each single mill can be considered to reflect the level of exposure near the discharge point, although there are two or more mills identified at a site.

The aquatic PECs calculated for the Benzidine-based Acid and Direct Dyes are summarized in Table 12 in the section on Characterization of Ecological Risk.

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Appendix C: Soil PEC Calculations for Benzidine-based Acid and Direct Dyes Used in Textile Dyeing

The method used for the stepwise estimation of the soil PECs from the textile wet processing sector and biosolids application is described as follows.

Step 1: Biosolids quantity

The quantity of biosolids produced from the wastewater treatment systems at the 33 sites evaluated for the aquatic exposure can be approximately assumed to equal the quantity of sludge generated. The quantity of sludge generated can be estimated from the per capita sludge production rate and the population served by the wastewater treatment systems. The per capita sludge production rate is reported as 0.090 kg/day per person from primary treatment and 0.115 kg/day per person from secondary treatment (Droste 1997). The combined population served by the wastewater treatment systems at the 33 sites is determined to be 5 661 000 persons based on the population served by each individual treatment system. This combined population is broken down into 1 810 000 persons serviced by primary treatment and 3 851 000 persons serviced by secondary treatment. The quantity of sludge generated or the quantity of biosolids produced is then estimated as:

Biosolids quantity = 0.090 kg/day per person × 1 810 000 persons + 0.115 kg/day per person × 3 851 000 persons = 605 765 kg/day = 221 104 000 kg/year

Step 2: Quantity of Benzidine-based Acid or Direct Dyes in biosolids

The quantity of Benzidine-based Acid or Direct Dyes in biosolids is estimated based on the maximum quantity of Benzidine-based Acid or Direct Dyes used for textile dyeing and the removal efficiency by wastewater treatment. The maximum quantity used for textile dyeing was estimated previously as 1900 kg/year for Benzidine-based Acid Dyes and 2500 kg/year for Benzidine-based Direct Dyes. The wastewater treatment removal by sludge sorption in the range of 40–80%, as reported for azo dyes by the Danish Environmental Protection Agency (Øllgaard et al. 1998), is considered applicable to both Benzidine-based Acid and Direct Dyes. An average removal rate of 60% is judged to be statistically representative of a large number of wastewater treatment operations across the sites of the 75 mills involving different treatment types and different individual azo dye substances. This removal rate is therefore used to estimate the quantity of Benzidine-based Acid or Direct Dyes in biosolids.

Quantity of Benzidine-based Acid Dyes in biosolids = 1900 kg/year × 60% = 1140 kg/year

Quantity of Benzidine-based Direct Dyes in biosolids = 2500 kg/year × 60% = 1500 kg/year

These estimated quantities are conservative, since they are not corrected for the amounts released to lagoons. In general, lagoons do not produce biosolids, and the amounts released to lagoons therefore do not end up in biosolids.

Step 3: Concentration of Benzidine-based Acid or Direct Dyes in biosolids

The concentration of the Benzidine-based Acid or Direct Dyes in biosolids is calculated by dividing the quantity in biosolids by the quantity of biosolids produced.

Concentration of Benzidine-based Acid Dyes in biosolids

= 1140 kg/year / 221 104 000 kg/year = 0.000 005 2 kg/kg = 5.2 mg/kg

Concentration of Benzidine-based Direct Dyes in biosolids

= 1500 kg/day / 221 104 000 kg/day = 0.000 006 8 kg/kg = 6.8 mg/kg

Step 4: Land application rate

The land application rate of municipal wastewater sludge (or biosolids) is regulated by the provinces and territories. The allowable annual limits on a dry weight basis are 1.6 tonnes/ha in Ontario, 3.4 tonnes/ha in British Columbia, 4.4 tonnes/ha in Quebec and 8.3 tonnes/ha in Alberta (Crechem 2005). The limit in Alberta is the highest in Canada and is used for soil exposure calculations.

Annual land application rate = 8.3 tonnes/ha = 0.83 kg/m2

Step 5: Quantity of Benzidine-based Acid or Direct Dyes over 10 years of biosolids application

The European Chemicals Agency (ECHA 2010) suggests using 10 consecutive years as a length of accumulation in evaluating soil exposure resulting from biosolids application. The quantity of the Benzidine-based Acid or Direct Dyes received per square metre of the amended soil during this 10-year period would be:

Quantity of Benzidine-based Acid Dyes per square metre of soil

= biosolids application rate × 10 years × concentration of Benzidine-based Acid Dyes in biosolids

= 0.83 kg/m2 per year × 10 years × 5.2 mg/kg = 43.2 mg/m2

Quantity of Benzidine-based Direct Dyes per square metre of soil

= biosolids application rate × 10 years × concentration of Benzidine-base Direct Dyes in biosolids

= 0.83 kg/m2 per year × 10 years × 6.8 mg/kg = 56.4 mg/m2

Step 6: Mass of ploughing-layer soil per square metre

The European Chemicals Agency (ECHA 2010) also suggests using 20 cm (i.e., 0.2 m) as the ploughing depth in determining a mixing layer. Using a dry soil density of 1200 kg/m3 (Williams 1999), the mass of the top 20 cm soil layer per square metre is:

Mass of ploughing layer per 1 m2 = 1200 kg/m3 × 1 m2 × 0.2 m = 240 kg/m2

Step 7: Soil PEC

The soil PEC is determined by dividing the quantity of the Benzidine-based Acid or Direct Dyes upon 10-year land application by the mass of ploughing-layer soil on a per square metre basis.

Soil PEC for Benzidine-based Acid Dyes = 43.2 mg/m2 / 240 kg/m2 = 0.18 mg/kg

Soil PEC for Benzidine-based Direct Dyes = 56.4 mg/m2 / 240 kg/m2 = 0.24 mg/kg

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Appendix D: Estimated Exposures to 3,3′-DMB from Polyamide Cooking Utensils

Exposures to 3,3′-DMB from use of black polyamide cooking utensils were estimated, based on information indicating that this substance can leach from the utensil to soup or sauce during use. Estimated exposures are based on the following assumptions: that an individual uses a polyamide black cooking utensil every day, that the leaching of 3,3′-DMB remains constant over multiple uses and that the utensil remains in the hot soup or sauce (while cooking) for a long period of time. Estimated daily intakes were derived using a detailed intake of foods (Health Canada 1998) and the median leaching level of 3,3′-DMB (based on the third extraction levels, using the LOD for non-detect utensils and an average volume:area ratio when not indicated) calculated from the Danish study (McCall et al. 2012).

Estimates are considered to be conservative, as leaching test conditions (3% volume per volume [v/v] aqueous acetic acid, 100°C, 30 minutes to 4 hours) are not truly representative of real use conditions; it is unlikely that all soups or sauces will be stirred continually for the entire duration of this length of time or at this temperature. As shown in the study, the concentration leaching out of these utensils is highly variable.

Estimated intake from a food item = [Chemical in food (µg/g) × Consumption (g/day)] / Body weight

3,3′-DMB in food (median leaching level):

3,3′-DMB in food = 1.4 µg/kg

Body weights (Health Canada 1998):

Infant (0–6 months): 7.5 kg

Toddler (0.5–4 years): 15.5 kg

Child (5–11 years): 21.0 kg

Teenager (12–19 years): 59.4 kg

Adult (20–59 years): 70.9 kg

Senior (60+ years): 72.0 kg

Conservative estimates of daily intakes of 3,3′-DMB from use of black polyamide cooking utensils are presented in Table D-1.

Table D-1. Consumption and estimated daily intakes of 3,3′-DMB from use of black polyamide cooking utensils

(a) 0–4 years
Food item 0–6 months: Consumption (g/day) 0–6 months: Intake
(µg/kg-bw per day)
0.5–4 years: Consumption (g/day) 0.5–4 years: Intake
(µg/kg-bw per day)
Soups, meat, canned 5.36 0.0010 41.64 0.0037
Soups, vegetable 4.97 0.0009 8.16 0.0007
Soups, tomato 1.91 0.0004 6.50 0.0006
Soups, dehydrated 0.33 0.0001 10.43 0.0009
Sauces and gravies 0.68 0.0001 5.64 0.0005
Total 13.24 0.0025 72.38 0.0065
(b) 5–19 years
Food item 5–11 years: Consumption (g/day) 5–11 years: Intake
(µg/kg-bw per day)
12–19 years: Consumption (g/day) 12–19 years: Intake
(µg/kg-bw per day)
Soups, meat, canned 41.76 0.0019 35.12 0.0008
Soups, vegetable 10.99 0.0005 21.88 0.0005
Soups, tomato 11.67 0.0005 6.95 0.0002
Soups, dehydrated 7.98 0.0004 7.91 0.0002
Sauces and gravies 8.98 0.0004 14.29 0.0003
Total 81.38 0.0036 86.15 0.0020
(c) 20–60+ years
Food item 20–59 years: Consumption (g/day) 20–59 years: Intake
(µg/kg-bw per day)
60+ years: Consumption (g/day) 60+ years: Intake
(µg/kg-bw per day)
Soups, meat, canned 55.29 0.0011 54.16 0.0010
Soups, vegetable 15.03 0.0003 18.17 0.0004
Soups, tomato 6.92 0.0001 7.93 0.0002
Soups, dehydrated 8.33 0.0002 5.70 0.0001
Sauces and gravies 14.82 0.0003 10.76 0.0002
Total 100.40 0.0020 96.72 0.0019

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Appendix E: Estimates of Exposure to Acid Red 97 from Textile and Leather Products

Table E-1. Estimated upper-bounding exposures to Acid Red 97 via contact with textile materials
Product scenario Daily exposure (mg/kg-bw per day)
Textiles; personal apparel (adult; dermal) 0.002 6
Textiles; baby sleeper (infant; dermal) 0.004 0
Textiles (infant; oral) 2.7 × 10−5

Dermal Exposure from Textile

Exposure estimate = [SA × AW × SCF × C × M × DA × F × P] / BW

Dermal exposure was estimated based on a scenario of full (100%) body coverage from wearing clothing to account for exposures from multiple pieces of apparel that cover the entire surface area of the body.

Oral Exposure from Textile

Exposure estimate = [SA × AW × SCF × C × M × F × P] / BW

Oral exposure to Acid Red 97 is estimated based on a scenario assuming that the infant is mouthing a textile object (e.g., blanket, textile toy) that may release Acid Red 97.

Parameters

SA: Total surface area = 18 200 cm2 (dermal; adult; personal apparel) and 3020 cm2 (dermal; infant; baby sleeper) (Health Canada 1998); 20 cm2 (oral; infant Zeilmaker et al. 2000).

AW: Area weight of textile = 20 mg/cm2 (US EPA 2012).

SCF: Skin contact factor = 1.

C: Concentration = 0.01 (unitless) (BfR 2007). Based on the default model developed by the “Textiles” Working Group established at the German Federal Institute for Risk Assessment (BfR 2007), assuming that a standard textile garment of 100 g/m2 is dyed with 1% active dye ingredient.

M: Migration fraction = 0.0005 (BfR 2007). The migration of azo dyes from textiles varies considerably depending on the type of fibre, the type of dye used, the dye load, dyeing technology and colour intensity and after treatment. The exposure from textiles is partly dictated by the amount of dye that migrates from textile material onto human skin (ETAD 1983) or via mouthing. The “Textiles” Working Group (BfR 2007) uses a peak initial migration of 0.5% to estimate exposure to dyes from newly bought unwashed garments, and the chronic migration rate is assumed to be one tenth of the value measured for the first migration to reflect exposure after initial washes. It is assumed that the sweat migration rate is similar to the salivary migration rate; this is consistent with observations of leaching behaviours of dyes from textiles reported by Zeilmaker et al. (1999). Accordingly, the fraction of dye that migrates from a textile material per wear is assumed to be 0.0005 for both dermal and oral exposure.

DA: Dermal absorption = 100%.

F: Frequency = 1×/day.

P: Probability that Acid Red 97 is present in textiles = 10%. In the RIVM risk assessment of azo dyes and aromatic amines from garments and footwear (Zeilmaker et al. 1999), the authors derived a chance of 8% for the appearance of carcinogenic azo dyes and aromatic amines in garments based on four European studies. The congener of Acid Red 97 is not an EU22 amine; the prevalence of this dye is not clear because there is limited product testing and monitoring on non-EU22 amines and associated dyes. From the limited data available (Danish EPA 1998; Brüschweiler et al. 2014), the detection of most non-EU22 amines in textiles is usually less than 10%. Accordingly, the presence of associated dyes in textiles would be the same or lower. The chances of an individual’s outfit containing Acid Red 97 every day are low. Given the conservatism used in other parameters in this exposure scenario (e.g. full body coverage), the probability that Acid Red 97 is present in a textile is assumed to be 10% in this screening assessment based on professional judgement.

BW: Body weight = 7.5 kg for infant, 70.9 kg for adult (Health Canada 1998).

Table E-2. Estimated upper-bounding exposures to Acid Red 97 from dermal contact with leather products
Product scenario Per event exposure (mg/kg-bw)
Shoes 5.8 × 10−2
Boots 1.9 × 10−2
Gloves 2.1 × 10−3
Jackets and coats 7.7 × 10−2
Trousers 5.0 × 10−2
Furniture 2.3 × 10−2
Toys 4.0 × 10−2

Dermal Exposure from Leather

Exposure estimate = [SA × AW × SCF × C × M × DA] / BW

Direct skin contact with articles of leather can result in dermal exposure to dyes used in leather dyeing. Of all the leather products considered, the potential drivers for exposure are presented below; furniture, apparel (e.g., jackets, trousers and gloves), footwear (e.g., shoes and boots) and toys, where it is assumed that direct contact with the infant’s palms can occur when playing with the toy. The exposure estimates presented below are considered upper-bounding based on conservative assumptions as well as not taking into account of a final application of a polyurethane sealant coating which would further reduce the consumer’s dermal exposure to the leather dye.

Parameters

SA: Surface area of skin contact (Health Canada 1998; Therapeutic Guidelines Ltd. 2008)

AW: Area weight of leather = 0.15 g/cm2 (Danish EPA 2012)

SCF: Skin contact factor

When the entire leather article is in direct contact with the skin, SCF is assumed to be 1. When the leather article is in indirect contact with the skin (e.g., shielding due to interior lining), SCF is assumed to be 0.1, which is a default value used to account for exposure due to diffusion of sweat-extracted dye from the leather material through the shielding fabric onto the skin (Zeilmaker et al. 1999). When a portion of the leather article is in direct contact and the remaining portion is in indirect contact, a weighted SCF is calculated: [(SAdirect × 1) + (SAindirect × 0.1)]/(SAtotal).

C: Concentration = 0.02 (unitless weight fraction) (Øllgaard et al. 1998)

M: Migration fraction = 0.1% (i.e., 39% over 365 days).

The dermal exposure to dyes from leather is partly dictated by the amount of dye that migrates from leather material onto human skin. Zeilmaker et al. (1999) measured the experimental leaching of azo dyes from leather footwear material to be 15% and 39%. The leaching was determined by extracting from 1 g of unwashed material from the upper side of a newly bought leather shoe with 100 mL sweat stimulant (extraction conditions: 16 hours at 37°C while shaking). These extraction conditions are expected to overestimate the migration of dyes from sweat. In estimating exposure to dyes from leather articles, it is assumed that 39% of the dye content leaches over one year and is available for dermal exposure, which would be equivalent to 0.1% leaching in one day.

DA: Dermal absorption = 100%.

BW: Body weight = 7.5 kg for infant, 70.9 kg for adult (Health Canada 1998).

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Appendix F: Benchmark Dose Calculations for 3,3′-DMOB·2HCl

Table F-1. Incidences of tumours in F344/N rats exposed to 3,3′-DMOB·2HCl (CAS RN 20325-40-0) in drinking water (NTP 1990)Footnote Appendix F Table F1 [a]
Tumours 0 ppm 80 ppm 170 ppm 330 ppm
Equivalent dose for male rats (mg/kg-bw per day) 0 6 12 21
Skin basal cell or sebaceous gland neoplasms 2/59 33/44 56/72 41/56
Skin squamous cell neoplasms 0/59 13/42 28/65 22/48
Zymbal gland neoplasms 0/58 10/45 25/75 30/60
Preputial gland adenoma or carcinoma 16/59 12/42 33/73 29/59
Oral papilloma or carcinoma 1/59 8/44 10/73 11/57
Small intestine neoplasms 0/59 4/44 7/75 5/60
Large intestine neoplasms 0/59 1/44 8/73 8/57
Liver neoplasms 1/58 4/39 7/54 8/35
Mesothelium 2/59 1/44 7/72 6/56
Equivalent dose for female (mg/kg-bw per day) 0 7 14 23
Zymbal gland neoplasms 1/60 12/45 21/74 16/59
Clitoral gland neoplasms 7/58 27/44 48/74 41/55
Mammary gland adenocarcinomas 1/60 2/45 14/73 20/57
Table F-2. BMD10 and BMDL10 calculations (mg/kg-bw per day) for neoplasms induced by 3,3′-DMOB·2HCl in male (MR) and female (FR) F344/N ratsFootnote Appendix F Table F2 [a]
Tumours Model name # of groups AIC P-value SRI BMR BMD BMDL
MR - Skin basal cell or sebaceous gland neoplasmsFootnote Appendix F Table F2 [b] LogLogistic 3 148.6 0.235 −0.015 0.1 0.32 0.22
MR - Skin squamous cell neoplasms Multistage 4 211.2 0.518 0 0.1 1.96 1.49
MR - Zymbal gland neoplasms Multistage cancer 4 225.6 0.952 0 0.1 2.98 2.44
MR - Preputial gland neoplasms Multistage cancer 4 306.7 0.572 −0.77 0.1 5.47 3.47
MR - Oral cavity neoplasms LogLogistic 4 174.1 0.097 −0.38 0.1 9.06 5.82
MR - Small intestine neoplasms LogLogistic 4 113.35 0.258 0.38 0.1 15.08 9.99
MR - Large intestine neoplasms Quantal-linear 4 109.3 0.811 0.63 0.1 13.63 9.37
MR - Liver neoplasms LogLogistic 4 119.4 0.880 −0.37 0.1 8.95 5.66
MR - Mesothelium Quantal-linear 4 116.55 0.528 −0.14 0.1 24.36 13.14
FR - Zymbal gland neoplasms LogLogistic 4 229.4 0.045 1.9 0.1 4.74 3.44
FR - Clitoral gland neoplasms LogLogistic 4 265.5 0.414 −0.11 0.1 0.91 0.66
FR - Mammary gland adenocarinomas LogProbit 4 177.9 0.692 0.26 0.1 10.70 8.21

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Appendix G: Benchmark Dose Calculations for 3,3′-DMB·2HCl

Table G-1.Incidences of tumours in F344/N rats exposed to 3,3′-DMB·2HCl (CAS RN 612-82-8) in drinking water (NTP 1991b)Footnote Appendix G Table G1 [a]
Tumours 0 ppm 30 ppm 70 ppm 150 ppm
Equivalent dose for male rats (mg/kg-bw per day) 0 1.8 4.0 11.2
Skin basal cell neoplasms 0/60 11/44 54/72 30/45
Skin sebaceous cell adenoma 0/60 0/44 7/72 5/49
Skin keratoacanthomas 1/60 1/44 8/67 5/27
Skin squamous cell neoplasms 0/60 2/45 17/74 27/59
Zymbal gland neoplasms 1/60 3/45 32/74 36/60
Preputial gland neoplasms 2/60 4/44 6/72 9/49
Liver neoplasms 0/60 0/45 35/72 33/55
Oral cavity neoplasms 0/60 0/44 4/67 5/32
Small intestine neoplasms 0/60 0/45 4/74 8/59
Large intestine neoplasms 0/60 0/45 6/67 15/38
Lung neoplasms 1/60 0/45 8/73 6/57
Equivalent dose for female (mg/kg-bw per day) 0 3.0 6.9 12.9
Skin basal cell neoplasms 0/60 3/45 10/69 9/46
Skin squamous cell neoplasms 0/60 3/45 9/72 12/55
Zymbal gland neoplasms 0/60 6/45 32/74 42/59
Clitoral gland neoplasms 0/60 14/45 42/73 32/58
Oral cavity neoplasms 0/60 3/45 9/73 13/59
Small intestine neoplasms 0/60 1/45 3/72 5/57
Large intestine neoplasms 0/60 1/45 7/70 4/46
Table G-2. BMD10 and BMDL10 calculations (mg/kg-bw per day) for neoplasms induced by 3,3′-DMB·2HCl in male (MR) and female (FR) F344/N ratsFootnote Appendix G Table G2 [a]
Tumours Model name # of groups AIC P-value SRI BMR BMD BMDL
MR - Skin basal cell neoplasmsFootnote Appendix G Table G2 [b] Multistage 3 134.5 1 0 0.1 1.07 0.51
MR - Skin sebaceous cell adenoma LogLogistic 4 85.17 0.24 −0.78 0.1 7.60 4.74
MR - Skin keratoacanthomas Multistage 4 100.2 0.48 0.81 0.1 5.24 3.24
MR - Skin squamous cell neoplasms Quantal-linear 4 181.6 0.62 1.15 0.1 1.91 1.51
MR - Preputial gland neoplasms LogLogistic 4 137.0 0.723 −0.35 0.1 7.11 3.87
MR - Oral cavity neoplasms Quantal-linear 4 62.3 0.748 0.267 0.1 7.83 4.74
MR - Small intestine neoplasms Quantal-linear 4 82.0 0.777 0.18 0.1 8.64 5.56
MR - Large intestine neoplasms LogProbit 4 96.4 0.732 0.439 0.1 4.57 3.45
FR - Skin basal cell neoplasms LogLogistic 4 126.9 0.961 0.33 0.1 5.06 3.50
FR - Skin squamous cell neoplasms LogLogistic 4 136.0 0.998 −0.11 0.1 5.16 3.62
FR - Zymbal gland neoplasms LogLogistic 4 211.4 0.999 −0.023 0.1 2.51 1.56
FR - Clitoral gland neoplasms LogLogistic 4 241.2 0.239 0 0.1 0.76 0.59
FR - Oral cavity neoplasms LogLogistic 4 140.8 0.996 −0.15 0.1 5.16 3.64
FR - Small intestine neoplasms Quantal-linear 4 70.5 0.997 0.1 0.1 15.48 9.37
FR - Large intestine neoplasms LogLogistic 4 85.9 0.645 0.75 0.1 10.18 6.39

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Appendix H: Benzidine Derivatives and Benzidine-based Substances with Human Health Effects of Concern

Some of the Benzidine Derivatives, Benzidine-based Acid Dyes, Benzidine-based Direct Dyes, and Benzidine-based Precursors in this assessment have human health effects of concern based on potential carcinogenicity. The details for supporting the potential carcinogenicity for these substances are outlined in section 7.2 Health Effects Assessment (see specific sub-sections), and generally based on one or more of the following lines of evidence:

Table H-1. Substances with human health effects of concern based on potential carcinogenicity
Substance Name/ acronym and CAS RN Classification for carcinogenicityFootnote Appendix H Table H1 [a] Evidence of carcino-genicity from animal studies and/or human epidemiology  Release of EU22 aromatic amine by azo bond cleavageFootnote Appendix H Table H1 [b] Read-across
Acid Red 128
6548-30-7
EU Category 1B carcinogenFootnote Appendix H Table H1 [c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
   3,3′-DMOB  
Acid Red 114
6459-94-5
IARC 2B,
EU Category 1B carcinogen[c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
x  3,3′-DMB  
Acid Black 209
68318-35-4
EU Category 1B carcinogen[c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
   3,3′-DMB  
NAAHD
68400-36-2
EU Category 1B carcinogen[c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
   3,3′-DMB  
Acid Red 99
3701-40-4
      release 2,2′-DMB by azo bond cleavageFootnote Appendix H Table H1 [d]
BADB
89923-60-4
      release 2,2′-DMB by azo bond cleavage[d]
Direct Red 28
573-58-0
IARC 1[c],
EU Category 1B carcinogen[c]
NTP “Known to be a human carcinogen”[c]
  Benzidine  
Direct Brown 95
16071-86-6
IARC 1[c],
EU Category 1B carcinogen[c]
NTP “Known to be a human carcinogen”[c]
x Benzidine  
Direct Blue 8
2429-71-2
EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
Direct Blue 15
2429-74-5
IARC 2B,
EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]
x 3,3′-DMOB  
Direct Blue 151
6449-35-0
EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
NAAH·3Li 67923-89-1 EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
BABHS
70210-28-5
EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
NADB·4Li 71550-22-6 EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
NADB·Li·3Na 75659-72-2 EU Category 1B carcinogen,  NTP “Reasonably anticipated to be a human carcinogen”   3,3′-DMOB  
NADB·2Li·2Na 75659-73-3 EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
NAAH·Li·2Na 75673-18-6 EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
NAAH·2Li·Na 75673-19-7 EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
NADB·2Li 75673-34-6 EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
NADB·Li·Na 75673-35-7 EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
NADB·3Li·Na 75752-17-9 EU Category 1B carcinogen[c],  NTP “Reasonably anticipated to be a human carcinogen”[c]   3,3′-DMOB  
Direct Blue 14
72-57-1
IARC 2B,
EU Category 1B carcinogen[c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
x 3,3′-DMB  
Direct Red 2
992-59-6
EU Category 1B carcinogen[c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
  3,3′-DMB  
Direct Blue 25
2150-54-1
EU Category 1B carcinogen[c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
  3,3′-DMB  
Direct Violet 28
6420-06-0
EU Category 1B carcinogen[c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
  3,3′-DMB  
Direct Blue 295
6420-22-0
EU Category 1B carcinogen[c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
  3,3′-DMB  
Direct Red 46
6548-29-4
    3,3′-DCB  
BAHSD
71215-83-3
      release 2,2′-DCB by azo bond cleavage[d]
TCDB
93940-21-7
EU Category 1B carcinogen[c],
NTP “Reasonably anticipated to be a human carcinogen”[c]
  3,3′-DMOB  
3,3′-DMOB
119-90-4
IARC 2B,
EU Category 1B carcinogen,  NTP “Reasonably anticipated to be a human carcinogen
x N/A
(EU22)
 
3,3′-DMB
119-93-7
IARC 2B,
EU Category 1B carcinogen,
NTP “Reasonably anticipated to be a human carcinogen”
x N/A
(EU22)
 
3,3′-DMB-2HClFootnote Appendix H Table H1 [e]
612-82-8
NTP “Reasonably anticipated to be a human carcinogen” x N/A
(HCl salt of EU22)
 

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