Musk Xylene Musk Ketone AHTN and HHCB in Sedimenting SPM

Extensive measurements of musk compounds in SPM were carried out in 5 .The SPM samples were obtained by sedimentation chambers made of Plexiglas (the sediment traps are described in 16 ). The surface water runs into the traps and its flow velocity is slowed down to about 1 cm s-1 making sedimentation possible. With a separation efficiency of 20-30 , the SPM was collected within four weeks yielding monthly mixed samples. In each case, two of these samples were mixed and subsequently analyzed....

Note on the HHCB Standard

The analytical standard of HHCB generally is not chemically pure but has only technical purity. In the past the standard material obtained by Promochem (Wesel, Germany) contained approximately 50 diethylphthalate according to the supplier's declaration. In many of the studies described in this chapter, the HHCB reference material was obtained by Promochem. Unfortunately, the HHCB impurity was not known and taken into account by all laboratories. As a consequence, the HHCB concentrations...

Water Samples

In the course of the surface water monitoring in 1996 7 , the water samples were analyzed by manual solid-phase microextraction (SPME) using 100 im polydi-methylsiloxane fibers. SPME with detection by gas chromatography-mass spectrometry (GC-MS) with selected ion monitoring (SIM) was found to be a rapid and reliable tool for the screening of synthetic musks in surface and sewage water samples 7 . Internal calibration with a suitable internal standard enabled reproducible quantification of nitro...

Subchronic Chronic Toxicity

At present, only limited data are available for assessing the risk to the aquatic environment, i.e., the populations of aquatic species exposed subchronically or chronically to low concentrations of parent compounds and metabolites of NMs and PCMs. In general, there are three potential adverse interactions of xenobio-tics with the health and sustainability of a population that are of primary importance (i) an extremely high incidence of pathological changes, e.g., tumors 32 resulting from...

Biotic and Abiotic Transformation Pathways of Synthetic Musks in the Aquatic Environment

Scarlett Biselli1 Robert Gatermann1 Roland Kallenborn2 Leiv K. Sydnes2 Heinrich H hnerfuss3 1 Dr. Wiertz-Dipl. Chem. Eggert-Dr. J rissen GmbH Analytical Laboratory (WEJ), Stenzelring 14b, 21107 Hamburg, Germany 2 The Polar Environmental Centre, Norwegian Institute for Air Research (NILU), 9296 Troms0, Norway 3 University of Hamburg, Institute of Organic Chemistry, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany Abstract Synthetic musks are being transformed to intermediates or relatively...

Synthetic Musks in Waste Water

A large part of the synthetic musk compounds is used as an additive to products intended for application in water. These are mainly cleaning agents and detergents and a number of articles for personal hygiene, which after their use are released at least partly into the waste water. Another part of these substances is retained in the washing or on the body, especially because synthetic musks are much less volatile than other fragrances of perfumery oils. Due to their higher adherence they tend...

The Role of Musk and Musk Compounds in the Fragrance Industry

Official Food and Veterinary Institute (LVUA) Schleswig-Holstein, Eckernf rder Stra e 421, Abstract An overview of the role of musk and musk compounds in the fragrance industry is given. Discovery and syntheses of representatives occurring naturally in animals and plants as well as of artificial substances possessing musk-like odor properties are reviewed. Examples of the three major classes - nitro musks, polycyclic musks, and macrocyclic musks - are covered. The importance of these compounds...

Determination of the Partition Coefficients

Partition coefficients of musk compounds have been determined in different solid matter matrices. The literature data are summarized in Table 5. In several field experiments, the partition of musk fragrances between SPM obtained by flow-through centrifuges and water was studied. The samples were Table 5 Partition coefficients between water and solid matter phase Partition coefficient based on organic Partition coefficient based on organic Partition coefficient based on organic taken from the...

Endocrine Modulation

Although the present database on potential endocrine modulating activity of NMs and PCMs is still rather scant,the compilation of mammalian data and data from in vitro assays with cells and tissue homogenates from aquatic species suffices for a primary assessment, at least of the potential (anti)estrogenic activity of these compounds. Neither subchronic or chronic administration of NMs, PCMs, or mixtures of NMs and PCMs 34,40,41 suggests any form of (antiestrogenic activity in rodent species....

Environmental Concentrations

Due to their application in detergents,household cleaning products and bath and hair care products, most of the production volume of the synthetic musks is released to the sewer after use. As a consequence, surface water concentrations of AHTN and HHCB are highly variable, from extremely low in remote areas (< 1 ng L1) to higher concentrations in rivers beyond the discharge points of sewage treatment plant effluents. The data of more than 200 surface water samples taken in Germany, The...

Summary of Experimental Toxicological Studies

The results of experimental toxicological studies show that musk compounds have generally a low acute toxicity. Oral LD50 ranged between 4 and 10 g kg-1 bw for nitro musks and between 0.5 and 5 g kg-1 bw for polycyclic musks with dermal LD50 showing even higher values. A lower acute oral toxicity was recorded for MA (0.3 g kg-1 bw) which is no longer in use. There is a very limited amount of experimental data on subchronic oral toxicity of nitro musks available in the open literature. In the...

Nitro Musks

MX and MK induce cytochrome P450 (CYP) enzymes in the mouse as well as in the rat. The enzyme induction pattern in the mouse is comparable to that of phenobarbital (PB), the classic CYP2B inducer and liver carcinogen in the mouse 21,65 (Table 1). In the rat liver MX induces phase-I cytochrome P450 oxidases (CYP1A, CYP2B) as well as phase-II metabolic enzymes such as cytosolic DT-diaphorase, glutathione-S-transferase (GST Ya subunit) and UDP-glucuronyl transferase. The activities of the latter...

Synthetic Musks in Ambient and Indoor

Roland Kallenborn1 Robert Gatermann2 1 Norwegian Institute for Air Research (NILU), The Polar Environmental Centre, NO-9296 Troms0, Norway 2 Dr. Wiertz - Dipl. Chem. Eggert - Dr. J rissen GmbH Analytical Laboratory (WEJ), Stenzelring 14b, 21107 Hamburg, Germany Abstract For the first time, the presence of synthetic musks is confirmed and investigated in air samples. New analytical methods are described developed for the purpose of ultra trace analysis of synthetic musks in low contaminated...

Musk Concentrations in Cosmetics and Household Products

According to surveys on the use of musks in fragrance products conducted by the industry, the most important source of exposure are skin creams because of their retention in the skin, followed by hydroalcoholic products (eaux de toilette) which have a high concentration of musk containing fragrances 5, 6 . On the other hand hygienic products such as soaps and bath foams, which are applied on large body area, will be washed off and are probably less important dermal source of musk compounds 6 ....

Perspectives

Due to critical public debates on the use of nitro musks and polycyclic musk compounds and the resulting regulatory limitations, the fragrance industry has put increasing emphasis on the development of macrocyclic and other musk odorants. A promising new class are the so-called linear musks. The first representative, a cyclopentenyl ester, was synthesized in 1975 and is being marketed as Cyclomusk. In 1990 another example (Helvetolide) of this class of compounds was discovered 61 . The future...

Results and Discussion

First, a scenario analysis is performed with EUSES to discover how spatial refinement can ameliorate the predicted concentrations. The Standard scenario uses the default values of EUSES, based on the generic region. In the NRW realistic scenario regional data characterising North Rhine-Westphalia (NRW) and more realistic emission data and partition coefficients are used. A third scenario is added containing the river Ruhr catchment and which represents a further step of refinement (Ruhr J). In...

Dietary Intake

The toxicological documentation required for a meaningful and reliable risk analysis of the synthetic musk compounds in the diet is at present inadequate. The most detailed experimental data were obtained from the toxicological studies with MX. Much less information is available on MK or polycyclic musk compounds AHTN and HHCB. Toxicological investigations of the other nitro and polycyclic musks are generally missing. Even where available, many studies with both the nitro and polycyclic musk...

Synthetic Musks in Drinking Water

The regulations and directives of the EU and the national legislation of the Member States set high standards for the quality of drinking water in terms of chemical and biological,but also organoleptic properties. These latter concern the flavor and odor as criteria for a high-quality drinking water. Studies on the threshold concentrations for the odor of fragrance substances in drinking water also included HHCB and AHTN 37 . The relatively low threshold concentrations of 80 ng L-1 HHCB and 40...

Toxicokinetics

Experimental studies on absorption, distribution, metabolism and excretion were conducted in laboratory animals after both the oral and dermal application. Seven days after a single po application of 3H-MX (70 mg kg-1 bw) to male Wistar rats the highest concentration of radioactivity was detected in the adipose tissue and the liver. The total residue of radioactivity in tissues was less than 2 of the administered dose. The major excretion route for MX was via bile into faeces. Urinary and...

Kp and Koc Values in Sludge

The partition coefficients obtained in the experiments with activated sludge were Kp 11,590 L kg-1 and Koc 63,660 L kg-1 for AHTN and Kp 13,600 L kg-1 and Koc 72,470 L kg-1 for HHCB 27 . The Kp as well as the Koc values for sludge are higher than the corresponding partition coefficients for SPM this is not surprising as sewage sludge and SPM represent different types of solid matter.

Enantiomeric Ratios of Hhcb Ahtn transATII and AHDI in Biota Samples

As an example for biota sample extracts, SIM fragmentograms are shown for tench and crucian carp in Fig. 4. Concentrations and enantiomeric ratios of HHCB, cis- and trans-HHCB, AHTN, trans-ATII and AHDI for 18 fish samples Fig. 4 SIM fragmentograms of tench and crucian carp sample extracts, stationary phase 1 1 mixture of OV from 20 Fig. 4 SIM fragmentograms of tench and crucian carp sample extracts, stationary phase 1 1 mixture of OV from 20 and 1 pooled mussel sample from the pond of the...

Toxicology of Synthetic Musk Compounds in Man and Animals

Hubertus Brunn1 Nikola Bitsch1 Judith Amberg-M ller2 1 Government Health Service Institute of Foodstuff and Veterinary Inspection, Marburger Strasse 54,35396 Gie en, Germany E-mail 2 Swiss Federal Office of Public Health, Food Toxicology Section, Stauffacherstrasse 101, 8004 Z rich, Switzerland Abstract Synthetic musk compounds (musk fragrances) are chemically heterogeneous compounds. The available toxicological data are incomplete. The NOAEL (No Observed Adverse Effect Level) values, obtained...

Polycyclic Musk Compounds

The polycyclic musk compounds were not discovered until the 1950s 5 . They are nitro-free substances, which can be divided into indane derivatives, tetraline derivatives, tricyclic compounds, and coumarin derivatives 6,29 . The most important representatives are listed in Table 3. Analogous to the nitro musk compounds they are artificial compounds which do not occur in nature and have no chemical relationship to the natural musk compounds. Their use began after the synthesis of (AHDI)...

Natural Musk

Deer Musk Price India

An animal secretion called musk is the carrier of the natural musk aroma. It is produced by the male musk deer (Moschus moschiferus L.) in a gland situated in the prenuptial region between the abdomen and the genitals 1,11-13 .The musk deer (Fig. 1) belongs to the family Moschidae and reaches approximately the size of the central European roe deer. It lives in upper regions of Eastern Asia, e.g., India, Tibet, China, Siberia, and Mongolia 3,11-15 . Fig. 1 Musk deer (Moschus moschiferus L.) 11...

Conclusions

In 1991, the first investigation of a synthetic musk compound (musk xylene) was conducted with fish samples from the Berlin area. In the meantime, several sewage sludge samples, 30 sewage samples, 132 surface water samples, 66 sediment samples, and more than 1500 fish tissue samples have been investigated for nitro musks and polycyclic musk compounds. In all compartments, HHCB was found to be the main contaminant among the synthetic musk compounds. Nevertheless, the distribution of the...

Enantioselective Analyses of Polycyclic Musks

The synthetic polycyclic musks HHCB e.g. galaxolide) and AHTN e.g.tonalide), which are important artificial fragrances used in a large number of perfumes, laundry detergents, fabric softeners, toiletry products, and other household products 25 , as well as the polycyclic musks ATII e.g. traseolide), and AHDI e.g. phantolide) were included in a recent study by Gatermann et al. 20 . The stereochemical structures of these four polycyclic musk compounds can be found in Fig. 1. All derivatives are...

Info

Fig. 6 The transformation of HHCB to HHCB-lactone from 18 Fig. 6 The transformation of HHCB to HHCB-lactone from 18 Fig. 7 SIM fragmentogram of a HHCB-lactone standard (ion 257) (top) standard mixture containing HHCB, AHTN, trans-ATII, and HHCB-lactone (TIC) stationary phase 1 1 mixture of OV (below) from 23,24 mum four peaks in the gas chromatogram. The enantioselective separation of this compound including the diastereomeric pairs of enantiomers was achieved using the same stationary phase as...

Transformation Pathways of Nitro Musk Compounds

The various mechanisms related to the reduction of nitrobenzene derivatives are well-documented in the literature and part of basic lectures of organic chemistry 3 . At low pH-values intermediates such as nitroso-benzene and N-phenyl-hydroxylamine may be encountered, with the final product benzeneamine (trivial name aniline). Under neutral or weakly acid conditions N-phenyl-hydroxyl-amine may dominate, while under basic conditions azoxybenzene, azobenzene and hydrazobenzene may appear or form...

Derivation of the PNEC

For an environmental risk assessment, environmental concentrations are compared to a predicted no-effect concentration (PNEC). The PNEC in the aquatic environment for AHTN and HHCB was derived with an assessment factor of 10 to the lowest NOEC in the data set 13 see Table 1. The PNECwater was 3.5 mg L-1 for AHTN and 6.8 mg L-1 for HHCB 11 . The PNEC for fish-eating predators was derived from a 90-day oral study on rats where the no adverse effect levels (NOAEL) were 15 mg AHTN kg-1 body-weight...

Synthetic Musks in House Dust

Fachbereich Chemie, Carl von Ossietzky University Oldenburg, PO Box 2503,26111 Oldenburg, Germany E-mail werner.butte uni-oldenburg.de Abstract House dust is a sink and repository for semi-volatile organic compounds and particle bound organic matter. Although data are available on the occurrence of pesticides, plasti-cizers, endocrine disrupters, and other organics that are persistent in house dust, reports on analytical methods and concentrations of synthetic musks in house dust are limited....

Macrocyclic Musk Compounds

The development of the macrocyclic musk compounds began in 1926 with the structural characterization of muscone and civetone by Ruzicka and others 15, 22,24-26 . They demonstrated the compounds to be cyclic macromolecules, the existence of which had been considered impossible according to the so-called Baeyer's strain theory 3,15,56 . After this breakthrough additional macrocyclic compounds exhibiting musklike odors were isolated from natural materials, their structures were elucidated, and...

Analysis of Synthetic Musks in Water Matrices

Polycyclic and nitro musk compounds are relatively low-molecular substances with molecular weights ranging between 200 and 300. They are sufficiently volatile and readily vaporizable without decomposition, thus complying with essential requirements of the gas chromatographic (GC) technique.A combination of gas chromatography with mass spectrometric detection (GC MS) is commonly used for the determination of polycyclic musks 8-10 . The EI mass spectra of polycyclic musks are adequately...

The Berlin Area

The contamination of the surface waters by municipal waste water discharges is of great relevance in the Berlin area. Thus, high concentrations of sewage contaminants are found in the receiving waters because of the high proportions of municipal sewage effluents in the surface waters. These high contamination levels result from low surface water flows and from the large amounts of raw sewage produced by its population of around four million people. Being situated in a densely populated area and...

Nitro Musk Compounds

The era of nitro musk compounds began with the discovery of the so-called Musc Baur by Baur at the end of the nineteenth century 19 . In the following years, other aromatic nitro compounds were synthesized, which gained considerable importance as replacements for natural musk. These artificial substances exhibit musk-like odors although they are structurally very different from the naturally occurring musk compounds 3,5,6,15 . The best known nitro musks (musk ketone, musk xylene, musk ambrette,...

Transformation Products of HHCB

Hhcb Synthesis

In 1997, first evidence about the presence of more polar chemical transformation products of HHCB and AHTN was obtained. However, no suggestions for chemical structures were offered 20 . In a pioneering work Franke et al. 21 elucidated the structure of the main HHCB-transformation product, -2-benzopyrane-1-one (Fig. 2 hereafter HHCB-lactone, sometimes referred to as galaxolidone), including its synthesis. Franke et al. 21 synthesised the racemic standard compound by oxidation of racemic HHCB...

References

Rimkus G, Gatermann R, Huhnerfuss H 1999 Toxicol Lett 111 5 2. OSPAR Convention for the Protection of the Marine Environment of the North East Atlantic. Working Group on Diffuse Sources DIFF , 6-9 Oct, 1998 Helsinki, Finland 3. Rimkus GG 1999 Toxicol Letters 111 37 4. Kafferlein HU, Goen T, Angerer J 1998 Crit Rev Toxicol 28 431 5. Ford RA 1998 Dtsch Lebensm-Rundsch 94 192 6. Ford RA 1998 Dtsch Lebensm-Rundsch 94 268 7. Minegishi K-I, Nambaru S, Fukuoka M, Tanaka A, Nishimaki-Mogami T 1991...