Synthetic Fragrances
Transcript of Synthetic Fragrances
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Synthetic Fragrances in the Aquatic Environment:
Overview of Chemistry,Monitoring, and Significance
Lantis I. Osemwengie, Ph.D. Environmental Chemistry Branch
Environmental Sciences DivisionNational Exposure Research Laboratory
Office of Research and DevelopmentEnvironmental Protection Agency
Las Vegas, Nevada 89119
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U .S. EPA N o t i c e
The U.S. Environmental ProtectionAgency (EPA), through its Office of
Research and Development (ORD),funded this research and approved thematerials that formed the basis for this
presentation. The actual presentation hasnot been peer reviewed by EPA. Mentionof trade names or commercial products
does not constitute endorsement orrecommendation by EPA for use.
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Overview
Synthetic musk compounds!
What are they?The chemistryMonitoring methods
Data evaluationSummary
Conclusion
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What are synthetic musk compounds
Polycyclic musks are acetylated andhighly methylated pyran, tetralin, andindane skeletons.
Nitro musks are methylated, nitrated,and acetylated benzene ring. They have the characteristic odor of
natural musks, hence the namesynthetic musk compounds.
Detergents, shampoo, bar soap, bodylotion, and additives for perfumes.
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Chemical Structures of Synthetic Polycyclic Musks
O
(HHCB)O
1,1,2,3,3,8-Hexamethyl-1,2,3,5,7,8-hexahydro-6-oxa-cyclopenta[ b]naphthalene
(AHTN)
O(AHMI)1-(1,1,2,3,3,6-Hexamethyl-indan-5-yl)-ethanone
O
O (ATII)
(DPMI)1-(3,5,5,6,8,8-Hexamethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-ethanone
1,1,2,3,3-Pentamethyl-1,2,3,5,6,7-hexahydro-inden-4-one
O
(AETT)
1-(3-Isopropyl-1,1,2,6-tetramethyl-indan-5-yl)-ethanone
1-(3-Ethyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-ethanone
O(ADBI)
1-(6- tert -Butyl-1,1-dimethyl-indan-4-yl)-ethanone
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Chemical Structures of Synthetic
Nitro Musks O 2N
OCH 3
NO 2 NO 2
NO 2 NO 2
MT
NO 2MMMA
2,6-dinitro-3-methoxy-4-tert-butyl toluene 1,1,3,3,5-Pentamethyl-4,6-dinitro-indan
NO 2O 2N
MX
1-tert-butyl-2,6-dinitro-3,4,5-trimethylbenzene
NO2O2N
NO 2
1- tert -Butyl-3,5-dimethyl-2,4,6-trinitro-benzene OMK
1-(4- tert -Butyl-2,6-dimethyl-3,5-dinitro-phenyl)-ethanone
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CH3
NO2
3)3
NO2
CH3
NO2
CH3
3)3
NO2
CH3
NO2
NO
CH3
NH
3)3
NO2
CH3
NO2
SO
Hb
CH3
NH2
3)3
NO2
CH3
NO2
h y
d r o l y s i s
H +
OH -
n i t r o r e d u c t a s e
o r D T - d i a p h o r a s e
MX Reactive metabolites
C(CH
C(CH
C(CH
C(CH
n i t
r o r e
d u c
t a s e
cysteine in haemoglobin
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Chemical Structures of Synthetic
Nitro Musk Metabolites
NO2O2N
NH24-AMX
4- tert -Butyl-2,6-dimethyl-3,5-dinitro-phenylamine
NH2O2N
2-AMX
NH2O2N
O2-AMK
NO 2 1-(3-Amino-4- tert -butyl-2,6-dimethyl-5-nitro-2- tert -Butyl-4,6-dimethyl-3,5-dinitro-phenylamine phenyl)-ethanone
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Physicochemical Properties of Synthetic Musks
OC L
a 4.80 a 258.4 C 18 H26 O 1.75a -4 72.7 a 33,200 h
a 4.86 a 258.4 C 18 H26 O 1.25a -2 68.2 a 33,700 h
b 3.90 d 244.4 C 17 H24 O-3 33,400 h
b 206.3 C 14 H22 O-1 1680 h
ADBI b 4.00 d 244.4 C 17 H24 O-3 13,300 h
b 3.72 d 258.4 C 18 H26 O 1.27b -3 - -
b 4.33 d 258.4 C 18 H26 O-2 - -
MX c 4.21 d 297.3 C 12 H15 N 3O 6 0.49c -6 4100 f
MK c 3.23 d 294.3 C 14 H18 N 2O 5 1.9c -6 1100 f
MM c 278.3 C 14 H18 N 2O 4 0.046c -4 1300 g
MA c 268.2 C 12 H16 N 2O 5 0.79c -4 646 g
B
267.3 C 12 H17 N 2O 4 4.08B -7
- --B 267.3 C 12 H17 N 3O 4 4.08
B -7 - -b 264.3 C 14 H20 N 2O 3
-8 - -
a: c:b:
OW
LogK MWT Empirical Water Solu. Henrys Law Vapor BCF(L/kg) (g/mole) Formula (mg/L) Constant* Pressure fish
(atm-L/mole) (mPa)
HHCB 5.9 7.56 x 10
AHTN 5.7 1.09 x 10
AHMI 5.9 -- 7.73 x 10 --
DPMI 5.9 -- -- 1.42 x 10 -
5.4 -- 7.05 x 10 --
AETT 5.7 9.96 x 10
ATII 6.3 -- 1.94 x 10
4.4 7.73 x 10 -
3.8 1.90 x 10 -
4.4 -- 1.54 x 10 -
4.0 -- 7.05 x 10 -
4-AMX 4.3 -- 3.79 x 102-AMX 4.3 -- 3.79 x 10
AMK 5.1 -- -- 9.30 x 10
M easured. Balk and Ford 1999 M easured. Schramm 1996 f: M easured. Yamagishi et al.1983Estimated. Osemwengie and Steinberg 2001 d: M easured. Winkler et al., 1998 g: Estimated Schramm 1996
B: Estimated. Behechti et al., 1998 *: Estimated. US. EPA EPI Suite h: Gey er et al., 1997
Acronym LogK
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Ubiquitous and Harmful
Effects in the Environment?
Industrial mass production . (Herren and Berset 2000) Persistent and bioconcentrate in fish tissues(G.G Rimkus, 1997)
Musk ambrette is known to cause testicularatrophy in laboratory rats (Davis, 1967)
Versalide is known to cause the paralysis ofthe hindlimbs in laboratory rats (Opdyke, 1979; Spenceret al., 1980)
Discoloration of internal organs in rats. (Opdyke1979)
MK negatively affects reproduction in
zebrafish (Carlsson et al., 2000)
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On-site Solid-phase Extraction Assembly
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On-site Solid-phase Extractionof 65 L of STP Effluent
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Monthly Collection of Eight Carp
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EPAs QA/QC manager monitored fish sampling
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-80 o C Storage Facility
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Gel permeation chromatography
showing residual lipids afterselective PLE system
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Galaxolide Fragmentation
C18
H26
O
O
O
HHH
H
H
+3
21330
.
258 M
243
M - CH
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Ion Chromatogram of Galaxolide present in fish tissues
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i ii )
0
10
20
3040
50
60
70
I ATII I
(
Mean Concentrat ons of Synthet c Musks Compoundsn STP Effluent (n=9
HHCB AHTN AHM ADB MX MK 4-AMX 2-AMX AMK
Musk Compounds
C o n c .
n g
/ L )
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i)
II 2
(
Mean Concentrations of Synthet c Musks in LakeMead Water (n=6
0.0
0.2
0.4
0.6
0.8
HHCB AHTN AHMI AT ADBI MX MK 4AMX AMX
AMK
Musks Compounds
C o n c .
n g
/ L )
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( )
0
5
10
15
2025
30
(
Mean Concentrations of Synthetic Musks in CarpFrom Lake Mead n=12
HHCB AHTN AHMI ATII ADBI MX MK 4-AMX 2-AMX AMK
Musk Compounds
C o n c .
n g
/ g )
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Regression Analysis
Musks in STP versus Musks in fish Using Statistical analysis system
(SAS) best fit regression lines wereobtained from the 12 months raw datafor musk conc. in STP effluent v. inLake Mead water.
Slopes and Y-intercepts for theregression lines were obtained for allmusk compounds.
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Concentration of Galaxolide (HHCB)in Lake Mead Water v. STP Effluent
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0
(
Y
R2
10 20 30 40 50 60 70 80 90 100 110 C o n c . n g /
L ) i n L a k e
M e a
d W a t e r
P re dic te d Y
= 0.78
P-value = 0.01
Conc. (ng/L) in STP effluent
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0.8
Concentration of 4-Amino Musk Xylenein Lake Mead Water v. STP Effluent
0
Y
R2 = 0.85
P-value = 0.009
0.1
0.2
0.3
0.4
0.5
0.6
0.7
L a
k e M e a
d ( n g
/ L )
Predicted Y
0 5 10 15 20
STP effluent (ng/L)
25
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----- ----- ----- ----- ----- ----- ----- ----- ---------- ----- ----- ----- ----- ----- ----- -----
----- ----- ----- ----- ----- ----- ---------- ----- ----- ----- ----- -----
----- ----- ----- ----- ---------- ----- ----- -----
----- ----- ---------------
-----
Cross-correlation of Synthetic Musks in Fish
Tissue (r-values)
MX MK HHCB AHMI ADBI ATII AHTN 4-AMX 2-AMXMXMK 0.81**HHCB 0.46AHMI 0.51ADBI 0.57ATII -0.10AHTN 0.354-AMX 0.68*2-AMX 0.44AMK 0.89*
0.75*0.96***
0.61-0.29
0.78**0.640.430.91
0.670.41-0.06
0.96***0.530.480.48
0.600.77*0.67*0.38
0.67*0.69
0.430.370.75
0.90**0.66
-0.140.490.500.08
0.490.390.32
0.83**0.47 0.18
* p < 0.05
** p < 0.01*** p < 0.001
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Summary
By understanding the chemistry of synthetic muskcompounds, we were able to determine theirpresence in environmental samples.
Enrichment factor approaches 10 6 : 1, we were ableto detect low concentrations of synthetic musk
compounds in Lake Mead. Performed statistical evaluation of raw data. Result suggests bioconcentration in carp.
Unable to provide definitive equation forconcentrations in STP v. fish.
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Conclusion
Developed extraction, clean-up, analysis, and
detection method for monitoring syntheticmusk compounds in aquatic environment.
HHCB can be predicted in the receiving
waters, using concentrations from the source. Variation in the concentrations of HHCB
(polycyclic musk) and MX (nitro musk) in
Lake Mead is a function of their levels in theSTP effluent.
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Acknowledgement
Dr Christian Daughton; U.S. EPA,NERL, ESD, ECB, Las Vegas, Nevada.
Dr Wayne Sovocool; U.S EPA, NERL,
ESD, ECB, Las Vegas, Nevada. Dr. Spencer Steinberg, University ofNevada-Las Vegas.