Synthetic Fragrances

8/14/2019 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.

Synthetic Fragrances

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