RTI/4948-31A-01FR June 19, 1992
POLAR ORGANIC COMPOUNDS IN FRAGRANCES OF CONSUMER PRODUCTS
FINAL REPORT
WORK ASSIGNMENT NO. IV-131
by
S. D. Cooper, J.H. Raymer, E. D. Pellizzari, K. W. Thomas, N. P. Castillo, and S. Maewall
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, NC 27709
RTI WOrk Assignment Leader J. H. Raymer
Contract Number 68-02-4544
Work Conducted Under Work Assignment Number: III-111
Project Officer: D. O. Hinton
EPA Work Assignment Manager: W. C. Nelson
Exposure Assessment Research Division
Atmospheric Research and Exposure Assessment Laboratory
Environmental Monitoring Branch
Prepared for
United States Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Submitted by: Approved by:
S.D Cooper E. D. Pellizzari, Ph. D.
Task Leader Project Director
J. H. Raymer, Ph.D.
Work Assignment Leader
NOTICE
This document is a preliminary draft. It has not been formally released by the U.S. Environmental Protection
Agency and should not at this stage be construed to represent Agency policy. It is being circulated for
comments on its technical merit and policy implications. Mention of trade names does not constitute
endorsement or recommendation for use.
ABSTRACT
The increasing use of fragrances in consumer products and the decreasing air exchange rate of buildings
has focused attention on the toxicological properties of fragrance compounds. The identities of compounds in
several representative consumer products were determined by a headspace collection technique using Tenax
sorbent trapping followed by gas chromatography/mass spectrometry and gas chromatography/high resolution
mass spectrometry analyses. The compounds identified by their mass spectra and by comparison to retention
times of standards were checked for their toxicological properties by use of an online computer search of
selected databases. These toxicological properties are listed in this report to the extent provided in the
available literature. Additional work was carried out to compare the relative recoveries of selected fragrance
compounds from Tenax-based sampling followed by gas chromatography/mass spectrometry analysis and
from canister-based sampling followed by gas chromatography/mass spectometry analysis.
TABLE OF CONTENTS
Section Page
Abstract ............................................................. ii
List of Figures ...................................................... iv
List of Tables ........................................................ v
1 Introduction ..................................................... 1-1
2 Conclusions ...................................................... 2-1
3 Recommendations .................................................. 3-1
4 Experimental ..................................................... 4-1
Product and Compound Selection ................................. 4-1
Compound Identifications by GC/MS and GC/HRMS .................. 4-2
Preparation of Standards ..................................... 4-2
Headspace Collection from Consumer Products .................. 4-2
Analysis by GC/MS ............................................ 4-3
Analysis by GC/HRMS .......................................... 4-3
Identification Criteria for Compounds in Consumer Products ... 4-4
Comparison of Recoveries of Polars--Tenax vs. Canister ......... 4-4
Analytical Procedures ........................................ 4-5
Calculations ................................................. 4-5
Literature Search .............................................. 4-6
5 Quality Assurance ................................................ 5-1
6 Results and Discussion ........................................... 6-1
Product and Compound Selection ................................. 6-1
Initial Analysis by GC/HRMS .................................. 6-1
Product and Compound Selection ............................... 6-2
Compound Identifications for Products .......................... 6-2
Recoveries of Polars from Air Sampling Media ................... 6-4
Literature Search for Toxicological Information ................ 6-6
7 References ....................................................... 7-1
Appendix A: IBM PC Computer Disk File of References Requested for
Retrieval ............................................... A-1
Appendix B: References for Toxicological Properties of Fragrance
Compounds ............................................... B-1
LIST OF FIGURES
Number Page
4-1 Schematic of apparatus used to collect headspace of the consumer
products .......................................................... 4-7
4-2 Analytical system schematic used for analyses of samples collected
by Tenax .......................................................... 4-10
6-1 Reconstructed ion chr-omatogram (mlz 35-350) of Giorgio Cologne for
Mean headspace analyzed by GC/MS. Numbered peaks are
referenced in Table 6-5 ........................................... 6-30
6-2 Reconstructed ion chromatogram (rnlz 35-350) of Chantilly Spray Mist
Cologne headspace analyzed by GC/MS. Numbered peaks are
referenced in Table 6-6 ........................................... 6-31
6-3 Reconstructed ion chromatogram (rnlz 35-350) of Giorgio Perfume
headspace analyzed by GC/MS. Numbered peaks are referenced
in Table 6-7 ...................................................... 6-32
6-4 Reconstructed ion chromatogram (nilz 35-350) of Coast soap
headspace analyzed by GC/MS. Numbered peaks are referenced
in Table 6-8 ...................................................... 6-33
6-5 Reconstructed ion chrornatogram (m/z 35-350) of Renuzk Freshell
air freshener headspace analyzed by GC/MS. Numbered peaks are
referenced in Table 6-9 ........................................... 6-34
6-6 Reconstructed ion chromtogram of Coast soap headspace analyzed by
GC/HRMS. Asterisks indicate peaks referenced in Table 6-8 ......... 6-35
LIST OF TABLES
Number Page
4-1 Headspace Generation System Operating Parameters .............. 4-8
4-2 GC/MS Analytical Conditions for Sample Analysis Using Tenax ... 4-9
4-3 GC/HRMS Analytical Conditions for Sample Analysis Using Tenax . 4-11
4-4 Analytical Conditions for Canister Sample Analysis ............ 4-12
6-1 Compounds Tentatively Identified by GC/HRMS As Part of Initial
Screening ..................................................... 6-10
6-2 Frequency and Level of Initially Identified Compounds in the
31 Consumer Products .......................................... 6-11
6-3 Polar Compounds Used in Standards for Analysis of Headspace
Samples ....................................................... 6-15
6-4 Headspace Generation and Collection Parameters used for the 5
Selected Consumer Products .................................... 6-17
6-5 Compounds Identified in the Headspace of Giorgio Cologne for
Men ........................................................... 6-18
6-6 Compounds Identified in the Headspace of Chantilly Spray Mist
Cologne ....................................................... 6-20
6-7 Compounds Identified in the Headspace of Giorgio Perfume ...... 6-23
6-8 Compounds Identified in the Headspace of Coast Soap ........... 6-26
6-9 Compounds Identffied in the Headspace of Renuzit Freshell Air
Freshener ..................................................... 6-28
6-10 Relative Recoveries of Polar Compounds from Canisters with
Respect to from Tenax-Mixture A ............................... 6-36
6-11 Relative Recoveries of Polar Compounds from Canisters with
Respect to from Tenax-Mixture B ............................... 6-37
6-12 Relative Recoveries of Polar Compounds from Canisters with
Respect to from Tenax-Mixture C ............................... 6-38
6-13 Relative Recoveries of Polar Compounds from Canisters with
Respect to from Tenax-Mixture D ............................... 6-39
6-14 Structures and Synonyms of Selected Fragrance Compounds ....... 6-40
6-15 Literature Search Procedure and Number of Citations Resulting . 6-45
6-16 Toxicological Properties of Ethanol ........................... 6-47
6-17 Toxicological Properties of Camphene .......................... 6-52
6-18 Toxicological Properties of Beta-Pinene ....................... 6-52
6-19 Toxicological Properties of Myrcene ........................... 6-52
6-20 Toxicological Properties of Benzaldehyde ...................... 6-53
6-21 Toxicological Properties of Limonene .......................... 6-54
6-22 Toxicological Properties of Beta-Phenethyl Alcohol ............ 6-55
6-23 Toxicological Properties of Chronellal ........................ 6-57
6-24 Toxicological Properlies of Camphor ........................... 6-58
6-25 Toxicological Properties for Benzyl Acetate ................... 6-60
6-26 Toxicological Properties of Estragole ......................... 6-61
6-27 Toxicological Properties of Cedrene ........................... 6-62
6-28 Toxicological Properties of Alpha-Pinene ...................... 6-62
6-29 Toxicological Properties of Diethylene Glycol Monoethyl Ether . 6-63
6-30 Toxicological Properties of Linalool .......................... 6-65
6-31 Toxicological Properties of Alpha-Terpineol ................... 6-66
6-32 Toxicological Properties of Beta-Citronellol .................. 6-66
6-33 Toxicological Properties of Menthyl Acetate ................... 6-67
6-34 Toxicological Properties of Acetone ........................... 6-68
6-35 Toxicological Properties of Tert-Butanol ...................... 6-71
6-36 Toxicological Properties of Ethyl Acetate ..................... 6-72
6-37 Toxicological Properties of 3-Octanone ........................ 6-74
6-38 Toxicological Properties of Cineole ........................... 6-74
6-39 Toxicological Properties of Phenylacetaldehyde ................ 6-75
SECTION 1
INTRODUCTION
Recently there has been increased interest in the emissions from consumer products. This increased interest
has resulted from several factors. First, the use of fragrances in consumer products has increased. This
increase in the use of fragrances causes a corresponding increase in exposure of persons to the polar
compounds used in the fragrances. Second, in the last two decades the trend toward energy efficient
buildings and homes has accelerated resulting in buildings with slower air exchange rates. This, in turn,
causes the concentration of air pollutants inside the building to increase. Third, some individuals have been
found to be sensitive to one or more of the compounds used in these fragrances. In some cases, individuals
have been forced to live or work elsewhere to alleviate symptoms believed to have been caused by indoor
pollutants. In light of these factors, there is interest in the ambient concentration levels and toxicological
properties of these fragrance components to determine if they pose risks to human health.
To better understand these potential risks, work was carried out in three areas. The initial aspect of this work
was to qualitatively identify the polar organic compounds in selected consumer products containing fragrances.
The selection of products to be tested was carried out in part by tabulating the complaints by individuals who
are apparently sensitive to certain consumer products as part of our previous work under Contract 68-02-4544,
Work Assignment 11-80. Gas chromatography/high resolution mass spectrometry (GC/HRMS) data from work
assignment 11-80 was evaluated to provide confirmation of the identities of compounds in ten consumer
products. Further identification of the compounds in five of the representative consumer products was also
carried out. Second, an initial comparison of the instrumental responses of polar compounds when collected
by Tenax GC or collected by Summa polished stainless steel canisters was made. This was done to evaluate
relative recoveries and to direct any further method development for the analysis of polars. Third, known health
risks were reviewed using an on-line computer search of the literature. Toxic effects from the compounds
identified from the consumer products could then be compiled. By addressing these issues, we hope to provide
a better understanding of the health risks of polar compounds and to identify further areas for research.
SECTION 2
CONCLUSIONS
The analysis of the headspace of five selected consumer products resulted in the identification of 25 compounds.
The consumer products selected for study contained a large group of the compounds tentatively identified in 31
consumer products in work conducted under contract 68-024544, work assignment 11-80. The 25 compounds
were identified using retention time and mass spectral matches to standard mixtures; most of these compounds
(19) were also confirmed by high resolution mass measurements of a major ion. The resulting identifications
indicated 8 alcohols, 3 aldehydes, 3 ketones, 3 ethers, 10 alkanes, and 3 esters, some of which are multifunctional.
The presence of these functionalities is probably representative of those expected since over half of the
chromatographic peaks were identified from the consumer products and the types of chemicals are those
expected in fragrances.The recovery of these compounds from stainless steel canisters was only fair overall
largely due to the higher molecular weights and therefore lower vapor pressures of the compounds. Since these
polar compounds are more likely to be strongly adsorbed to a surface than are volatile organic compounds
(VOCs), this lower overall relative recovery is not surprising. Unfortunately the relative recovery data did not
clearly support which is the better of the sampling media for these fragrance compounds, Tenax or canisters.
The search into the toxicological properties of the 25 compounds revealed a paucity of available data for most
compounds reviewed. The literature data that was found tended to suggest relatively low toxicities overall;
however some compounds were found to give positive results for toxic effects at low doses. One issue not
addressed is that of special sensitivities (e.g., rashes) of specific individuals to certain compounds or
fragrances. Investigation of this issue is essentially in its infancy and will need to be pursued further to determine
the extent of this problem.
SECTION 3
RECOMMENDATIONS
The collected data shows that there are some toxic effects that occur at low, and potentially environmental,
levels. It is probable that the toxic effects noted are those which are expected for a given compound of interest
based on structure-activity relationships, etc. Toxic effects not tested may or may not indicate a likelihood of
toxicity.
To test whether the known toxic effects are important with regard to human health, a simple analysis of the
products (instead of their headspace) would be helpful in understanding the percent present in the different
products. This would provide an estimate of the theoretical abundance of each fragrance compound in air.
If this theoretical concentration surpasses that of any concentration at which a toxic effect occurs then it is
worthwhile to develop and validate a method for the analysis of these compounds. For persons exhibiting
a high degree of sensitivity toward fragrance compounds, a more clear understanding of the mechanisms
of the toxic effects will need to be developed in order to understand and to quantify this sensitivity. Until then
the medical community will continue to debate whether these effects are truly real or imagined.
SECTION 4
EXPERIMENTAL
PRODUCT AND COMPOUND SELECTION
As part of the determination of the compounds present in the consumer products, work carried out in work
assignment II-80 was completed. Specifically, GC/HRMS data was obtained from ten of the 31 consumer
products screened by low resolution mass spectrometry and was provided to a chemist with experience in
mass spectral interpretation. The data provided included one high resolution mass measurement of either
the parent ion or a major fragment. This allowed an assignment of the empirical formula by matching the
closest mass of a formula to the actual incurred mass of the unknown peak. For this purpose only formulas
using C, H and O with up to 20, 42 and 8 atoms, respectively, were used. Additionally low resolution mass
spectra of these peaks were also provided. Analytical details are provided in a subsequent sub-section.
The consumer products selected for further evaluations were taken from the ten consumer products initially
analyzed by GC/HRMS. Using the data from low resolution gas chromatography/mass spectrometry (GC/MS),
the compounds found in one or more of the 31 consumer products were tabulated. The frequency and relative
intensity at which the compounds occurred across all 31 products were used to help select five products for
further evaluation. Products with compounds which occur frequently and/or at higher relative concentrations
were of greater interest. Additionally, the five products were chosen to assure that a wide range of analytes
found across all products would be targeted. This strategy would best represent consumer products as a whole.
This strategy made the solution of the analytes for preparation of standards straightforward. Polar compounds
not available commercially were dropped from consideration. Those occurring in the five products chosen and
commercially available were ordered.
COMPOUND IDENTIFICATIONS BY GC/MS AND GC/HRMS
Preparation of Standards
Standards of the compounds selected for use in the analysis of headspace of consumer products were
prepared and used to confirm identities in the consumer products. The first step was to group the compounds
so that closely eluting analytes would be prepared in separate standard mixtures. Additionally, compounds
with similar mass spectra were similarly placed in separate mixtures to avoid ambiguity, particularly if the
empirical formulas were identical. Ideally mixtures were prepared with 10 to 16 compounds each.
Mixtures were prepared gravimetrically, except for compounds more volatile than hexane. These volatile
components were added to the septum sealed vial by volume using a syringe, so their percentage of the
mixture is less precise. Once prepared and mixed, a 1.00-mL aliquot of the mixture was weighed to determine
the density allowing concentrations to be calculated. Each concentration in the mixture was calculated from
the equation:
ma
Ca = --------------
(sum mi) / d
where Ca is the concentration of analyte a, mi is the mass of analyte i and d is the density of the mixture.
When volumes of certain analytes were added, their individual masses were estimated from literature densities.
Dilutions of the mixtures in methanol were also prepared to allow loading of the analytes onto Tenax cartridges
by a flash evaporative technique. The preparation of Tenax cartridges and loading of analytes onto Tenax
cartridges by flash evaporation has been previously described [1].
Headspace Collection from Consumer Products
In order to evaluate the organic vapors given off by consumer products, a headspace generation system was
used to allow collection of the vapors. The schematic of the system is shown in Figure 4-1. In operation, a small
amount of the product was placed into a headspace purge vessel, then humidified nitrogen was swept through
the vessel. This provided a gas stream that could be sampled by Tenax cartridges.
The parameters used for operating the system are shown in Table 4-1. It operated by providing a slightly
humidified stream of N2, which was then directed through a gas port in the headspace purge vessel.
Once started, the gas stream immediately was collected by the Tenax cartridges after being filtered by glass
fiber filters. The filters eliminated any problems caused by collection of particles by the Tenax cartridge.
Any excess flow from the headspace vessel was vented. Varying amounts of product were used and these
amounts are described in the Results section. These amounts were not completely sampled. The flow was
continued for 2.5 to 3.75 minutes.
Analysis by GC/MS
Analysis of the consumer product headspace sample and standards was carried out by GC/MS in order to
identify standard components in the headspace samples. A schematic of the analytical instrument used is
shown in Figure 4-2 for both GC/MS and GC/HRMS systems. Through the use of matching retention times
and mass spectra, strong evidence for identifications could be acquired.
The Tenax cartridges were loaded with the following external standards before analysis [2]: perflurobenzene (PFB),
perfluorotoluene (PF-0 and bromopentafluorobenzene. All cartridges were analyzed using standard analytical
parameters shown in Table 4-2. The data was manually interpreted and compared to provide the identifications
of the compounds.
Analysis by GC/HRMS
Analysis of a parallel set of samples and standards was carried out by GC/HRMS to verify the identification of
compounds by GC/MS. This technique provided not only mass spectral confirmation by a second instrument,
but also provided a reasonable empirical formula for a parent ion or major fragment.
Since a mass calibrant gas is constantly bled into the mass spectrometer, the Tenax cartridges with headspace
samples were loaded with approximately three times the levels used for GC/MS. This provided sufficient signal
to noise to provide quality data. The Tenax cartridges were all loaded with the three external standards as for
GC/MS. All cartridges were analyzed using the analytical parameters shown in Table 4-3. The data was manually
interpreted and compared to provide the identifications of the compounds.
Identification Criteria for Compounds in Consumer Products
All identifications of mass spectra were carried out by manual interpretation. There were two levels of
identification for the polar compounds: tentative and confirmed. A compound with a confirmed identfty had
the following:
- retention time match of peak between standard and headspace sample
- mass spectral match between standard, headspace sample and library spectrum for both GC/MS
and GC/HRMS
- matching empirical formula obtained from GC/HRMS theoretical and actual masses
- adequate intensity of spectral components for identification.
The tentative identification lacked a good spectral match between the standard and headspace sample peak
for one of the two instruments (GC/MS or GC/HRMS).
COMPARISON OF RECOVERIES OF POLARS--TENAX VS. CANISTER
One of the primary goals of this study was to evaluate the ability of Summa treated stainless steel (S.S.)
canisters to collect polar compounds quantitatively. This was evaluated with respect to collection by Tenax
cartridges. The subsequent analysis steps for each collection technique would also contribute to the overall
ability to quantitatively analyze air for polars.
Analytical Procedures
The standard mixtures prepared for standards preparation in the qualitative analysis work were also used to
prepare standards using Tenax or S.S. canisters. Tenax cartridges were loaded so that approximately
100 ng/analyte was loaded. Canisters were loaded using normal loading procedures [3] to generate
concentrations of each anatyte at - 80-100 ng/L. The external standards PFB and PFT were added for both
Tenax and canisters to assure that comparisons were valid. The Tenax standards were analyzed as for the
previously described GC/MS analysis so analysis procedures are not discussed further. The standards in S.S.
canisters were analyzed by a second GC/MS instrument in a similar manner and the parameters used are in
Table 4-4.
Calculations
The relative recovery of analytes, or more accurately the relative response of analytes, with regard to canister
vs. Tenax was calculated by using a major ion of each analyte. The ion used for the external standard, PFB,
was m/z 186. The means of calculating relative recovery was through the use of the following equation:
% Relative Response = 100 - (Acanister / ATenax)
where
(analyte/PFB186)response
A = -------------------------
(analyte/PFB186)mass
The ratio (analyte/PFB186)response refers to the area response of the analyte ion chosen to m/z 186 of PFB.
The mass ratio is calculated from the respective amounts injected. By comparing Acanister to ATenax a relative
recovery can be estimated. To assess variability in the data, each standard was analyzed twice for each
technique.
LITERATURE SEARCH
One of the primary components of investigation was to evaluate the toxic effects of the identified polar
compounds found in the consumer products selected. This search was conducted using on-line computer
database using keywords, compound names and Chemical Abstract Service (CAS) registry numbers.
The databases chosen for the search are part of Dialog and are: CAS, ToxLine, CancerLit and RTECS
(Registry of Toxic Effects of Chemical Substances). The latter three databases are maintained by the
National Library of Medicine (NLM). An additional reference used for citations on cancer is published by
the National Institute of Health [4]. The general strategy for selecting references was to search under the
compound name, the CAS registry number(s) and using keywords (i.e., toxic, carcinogen, mutagen, irritant,
teratogen). For the three databases by NLM, no keywords were used since most references essentially
concern health effects. For the CAS database, the keywords were used and compared to a comprehensive
manual search over the past 25 years of literature for one compound to assure as efficient a search as possible.
Tables 4-1 - 4-4 omitted
SECTION 5
QUALITY ASSURANCE
This study was conducted as part of the first phase of Work Assignment III-111. A QAPP was not required by
the Project Officer. Quality assurance activities conducted in support of this work assignment included meetings
and discussions with study staff concerning data quality and systems audits. Systems audits and data review
were conducted to ascertain that the data reported accurately reflect the raw data collected and that the methods
and procedures used are accurately reported.
Quality control procedures were included in the sampling and analysis phases of this study. In addition, quality
control samples (blanks and replicates) were analyzed as a part of the study.
| 1. |
Qualitative analysis using GC/low resolution MS
The tune and mass calibration of the instrument were verified according to established SOPs.
Standards were analyzed to establish a database of spectra and retention times. Identifications
of compounds in consumer products were based on matching spectra and retention times.
Blanks were analyzed to monitor background. |
| 2. |
Qualitative analysis using GC/high resolution MS
Tune and mass calibration of the instrument were verified using established SOPs. Mass calibration was
also verified using the standards PFB or PFT. Standards were analyzed to establish a database of retention
times and exact mass measurements. Identification of compounds in consumer products was based on
matching retention times and exact mass measurement (± 30 ppm). Blanks were analyzed to monitoring
background. |
| 3. |
Quantitative analysis (Tenax) using GC/MS
The tune and mass calibration of the instrument were verified daily according to established SOPs. Overall
performance was assessed by monitoring the spectrum and response (peak area) of the external standards
PFB and PFT which were loaded onto each Tenax cartridge. Tenax was cleaned, cartridges prepared and
tested according to established SOPs. Preparation of fragrance standard cartridges and loading of the
external standards PFB and PFT was also carried out using established SOPs. The fragrance standard
cartridges were prepared and analyzed in duplicate (4 mixtures). Experiments were comparing Tenax and
canisters conducted in duplicate in order to assess overall precision. The experimental results are shown in
Table 6-10. The results are intended to show relationship between analysis of Tenax and canister samples,
but not to determine experimental accuracy of precision. |
| 4. |
Quantitative Analysis (canister) using GC/MS
The tune and mass calibration of the GC/MS system analysis began. Instrument performance was monitored
by recording response peak area) of the external standards for each analysis.
Canisters were cleaned and tested for background before use. Primary standard canisters were loaded
from gravimetrically-prepared standard mixes (4). Two calibration standard canisters were prepared and
analyzed from each primary standard canister. External standards were prepared in a canister and an
aliquot was co-injected with each standard and sample for analysis. |
SECTION 6
RESULTS AND DISCUSSION
PRODUCT AND COMPOUND SELECTION
Initial Analysis by GC/HRMS
Initial work as part of work assignment II-80 included the GC/HRMS analysis of ten of the 31 consumer products
originally screened. The ten products whose headspace was analyzed were:
- Giorgio cologne for men
- Chantilly spray mist
- Giorgio perfume
- Aqua Net hairspray
- Coast soap
- Renuzit Freshell air freshener
- Downy fabric softener
- Sure solid deodorant/anti-perspirant
- Vaseline Intensive Care lotion
- Max Factor nail enamel remover
These products were chosen to include a range of polar compounds across the volatility range and also to
focus on polars that are likely to be more prevalent and in these products. The analysis by GC/HRMS indicated
a relatively small number of compounds as shown in Table 6-1. This small number was due to a relatively low
signal-to-noise ratio caused by the relative level of calibrant gas used in the instrument. In spite of this, a number
of common fragrance constituents were found. It should be noted that standards of these compounds were not
analyzed at this stage so the list of identified compounds is tentative.
Product and Compund Selection
To provide strong evidence of compound identifications in the consumer product headspace analysis, work
was more intensely focused on the analysis of five products and a number of expected polar constituents.
The five consumer products selected are below:
- Giorgio cologne for men
- Chantilly spray mist cologne
- Giorgio perfume
- Coast soap
- Renuzit Freshell air freshener
By using the analysis results of the previous work assignment (II-80), a table of frequency in the 31 products and
relative intensity (Table 6-2) provided important information to determine both the consumer products and polar
compounds to be targeted. The more frequent or more intense level compounds in Table 6-2 were chosen as
well as the products that contained them. The subsequent list of compounds selected and those that were
available for this task are shown in Table 6-3. Some volatile organic compounds (VOCs) were included as they
were expected and they also are known to recover well during analytical procedures. The CAS registry numbers
provided are for the general form if an optically active form exists. Additional CAS numbers in those cases will
include a racemic mixture number, a (+) and a (-) number when one chiral center exists. These numbers were
used as readily available for literature searching purposes. The order for each of the four mixtures is the elution
order for a DB-624 column.
COMPOUND IDENTIFICATIONS FOR PRODUCTS
The analysis of the standards loaded onto Tenax cartridges and the headspace samples loaded onto Tenax
cartridges allowed compound identifications to be made. The collection parameters used, shown in Table 6-4,
provided sufficient levels of each product's headspace to yield good quality mass spectra. The blanks loaded at
higher volumes showed no significant levels of compounds upon analysis. The low level samples were analyzed
by the GC/MS, however, the high level samples were analyzed by the GC/HRMS to overcome the bleed of the
perfluorokerosene (PFK). The compounds identified in the headspace samples of the five consumer products
are shown in Tables 6-5 through 6-9. Corresponding chromatograms are provided in Figures 6-1 through 6-5,
respectively, as analyzed by low resolution GC/MS.
The compounds listed in the tables were identified by low resolution mass spectra whether they were compared
to mass spectra of standards or literature mass spectra. All compounds listed have clean (background free of
interferences) spectra to assure that identifications are accurate. The peak number refers to the sequence of
peaks identified by low resolution GC/MS in Figures 6-1 through 6-5. The spectrum number is provided in one
case for comparison purposes. The MS data provided is derived from the GC/MS unless no retention time is
given; it is provided from the GC/HRMS otherwise. When a compound present in a standard was analyzed
successfully it's eight most intense ions plus the parent ion were used for spectral comparison purposes.
The relative intensities of the standard and the unknown (product headspace) are given in parenthesis. If no
standards were analyzed for identified compounds, the eight most intense ions and the present ion were
provided for the product headspace.
The high resolution mass spectral data are provided for the components where spectral and ion intensities
were adequate and is based on the corresponding formula provided. The actual mass measured deviated
from this theoretical value by the ppm indicated. For example, an ion with a theoretical mass of 100.00000
amu having a ppm deviation of 1.0 had an actual measured mass of 100.00010 amu. The window used to
determine a formula match was ± 30 ppm. Values are provided for many of the standards but are useful
primarily to confirm the standards identities. The values for the unknowns are of much greater value for
identification purposes. Overall the components identified with the highest degree of certainty are listed first
followed by identification of lesser certainty. Components with no standard analysis were identified with the
least certainty and are shown at the bottom of the tables.
As can be seen in the chromatograms of the product headspace samples, a majority of the major components
were identified at least by obtaining a clear spectrum which was matched to a literature spectrum. However, as
the tables of the identifications for the products indicates most of the identifications were made with comparison
of retention times and low resolution spectra. Spectra were not considered reliable either because of poor
spectra due to background or difficulty in interpretation. The latter reason occurred due to collection of
components, lack of literature spectra (in the cases for compounds not in standards) and ambiguous spectra.
Components whose identities were corroborated by high resolution mass measurements had the highest
degree of certainty. Most of those mass measurements were for the parent ion providing an unambiguous
molecular formula. The remainder were of major fragment ions providing a slightly lower degree of certainty.
These formulas were for O-20 carbon atoms, O-42 hydrogen atoms, and O-8 oxygen atoms. The closest match
was used if more than one was given and nonsense formulas were discarded.
A comparison of the chromatograms in Figures 6-4 and 6-6 shows the similarities and differences between
the two instruments used. Typically the compounds which were early eluters on the GC/HRMS were not found,
probably due to poor signal-to-noise caused by the addition of calibrant gas to the HRMS. Overall though the
pattern is similar and the retentions tend to track each other with approximately a 2-min difference between
instruments.
RECOVERIES OF POLARS FROM AIR SAMPLING MEDIA
In order to evaluate the analysis of standards of the polar analytes, the four standard mixtures were loaded in
duplicate into stainless steel canisters and onto Tenax cartridges. These standards were then analyzed and
the response of the compounds quantitated relative to added external standards. The data were then tabulated
to provide relative recoveries using S.S. canisters with respect to Tenax GC. These results are shown in
Tables 6-10 through 6-13.
Interpreting these results is difficult, particularly as many compounds responses were not calculated. It should
be noted no benzaldazine standard was ever detected. Also, a zero in these tables indicates not detected in the
canister standard, but detected in the Tenax standards. Secondly, the reproducibility was not as high as
desired. However, by examining the relative recoveries of the more traditional pollutants (e.g. toluene) then
some understanding of the difference can be determined. It should be noted for all mixtures the compounds
are listed in order of retention with the last two being the external standard (PFT) and its alternate (PFB).
Structures and formulas are provided in Table 6-14. Across all mixtures ft can be seen that the higher molecular
weight compounds (eluting later) are recovered poorly, if at all. As for chemical classes, ketones of moderate
molecular weight were recovered, reasonably well. Aldehydes and alcohols were generally poorly recovered
and esters were variable. The alkanes appear to be recovered reasonably well but are somewhat variable also.
This variability tends to point to standard preparation and analysis procedures which were not in control for
many polars, however, this is tempered by variable results for toluene and PFT. In fact, PFT results indicate it
may have been a better external standard. Overall the results indicate that the higher molecular weight
compounds do not recover well in general. For this application then, Tenax is probably superior for the purpose
of sampling for fragrance components in consumer products, though the variability of results make this
conclusion tentative.
This uncertainty points out the need to develop properly validated methods for the quantitation of these polar
compounds. Without a method to quantify these polars any comparison does not have a true yardstick to
measure against. It is unlikely that evacuated canisters could be used without heating as many of the molecular
weights and boiling points of the target compounds are elevated relative to VOCs. Some compounds can
also exhibit degradation under certain conditions. Therefore, for these reasons a validated method for sampling
and analysis of these polar compounds is recommended.
LITERATURE SEARCH FOR TOXICOLOGICAL INFORMATION
In order to better assess the risks of exposure to the use and application of the selected consumer products,
a literature search was undertaken to find and retrieve journal articles providing toxicological information for
the identified compounds. The compounds selected were those found in at least one of the five products
analyzed and for which a standard was analyzed. These compounds were grouped into 2 groups: confirmed
and tentative. A confirmed identity is one with the following: standard and unknown retentions match by GC/MS
or GC/HRMS, low resolution spectra of the standard and unknown match by GC/MS or GC/HRMS, and a
high resolution mass measurement was made for the unknown (efther parent or major fragment). A tentative
identity is made as for the confirmed identity except no high resolution mass measurements were made on the
unknown peak. Using these criteria the following lists of identities were made.
Compounds Identified - Confirmed
- ethanol
- camphene
- Beta-pinene
- Beta-myrcene
- benzaldehyde
- limonene
- benzyl alcohol
- Beta-phenethyl alcohol
- citronellal
- camphor
- benzyl acetate
- estragole
- Alpha-cedrene
- Alpha-pinene
- diethylene glycol mnoethyl ether
- linalool
- Alpha-terpineol
- Beta-citronellol
Compounds Identified - Tentative
- acetone
- t-butanol
- ethyl acetate
- toluene*
- 3-octanone
- cineole
- 2-ethyl-1-hexanol*
- phenylacetaidehyde
- terpinen-4-ol*
- menthyl acetate
References having toxicological properties of these compounds, whether confirmed or tentative identities,
were gathered by an electronic literature search method. The three exceptions to this search list were: toluene,
2-ethyl-l-hexanol, and terpinen-4-ol. Toluene's properties are already well known as it is a widely used industrial
solvent. The other two were omitted from the search.
As noted in the experimental section, the databases chosen for the search were CAS, ToxLine, CancerLh,
and RTECS. To assure that electronic searching was effective, a manual search of references containing
toxicological data for Alpha-pinene was conducted. This check indicated that the electronic search was
effective at finding approximately 75% determined by manual search and a few extra references as well.
The electronic search was conducted through Dialog OneSearch, which allowed an efficient retrieval of
references by retrieving all pertinent references from ToxLine and MedLine that did not overlap, then retrieving
references in CAS that were not previously retrieved from ToxLine and CancerLit. This significantly reduced
retrieval costs as CAS is more expensive per reference.
As noted in the experimental section, several keywords were used in the search in CAS. Since some
compounds have thousands of references, some additional keywords were used to filter the references further.
The different search procedures used are listed below and they were used for each compound as indicated in
Table 6-15.
Also given in the table are the number of references found in the literature search. A manual review of the title
(and abstract if retrieved) resulted in a fraction of the articles which were selected for retrieval. The numbers of
citations selected for each compound are also indicated in Table 6-15. Most of these articles were retrieved
and reviewed for toxicological information [5-370]. A listing of the requested references (cited in CAS, ToxLine
and CancerLk) are provided on magnetic disk with this report which is taken directly from the computer search
information retrieval (Appendix A). This is a subset of all of the references listed in the computer search. All of
this information along with the RTECS data provided the total information gathered in the search for toxicological
data. It should be pointed out that articles not referenced in RTECS, not in English, and are published before
1965 were not retrieved using this search procedure. Additional references on cancer-causing effects were also
obtained from a compilation by the Public Heafth Service and the National Cancer Institute [4].
The compilation of the references of the toxicological data is provided in Appendix B. These two tables quickly
allow one to determine the number of references which were found in each category of toxic effects for each
compounds. In many cases data was not found in the literature and are marked with dashes. Also some citations
were negative results (i.e., no toxic effect(s) observed at the dose administered) so a few references is not
necessarily an indication of toxicity.
The compilation of effects, given in a format similar to RTECS is provided in Tables 6-16 through 6-39.
The toxic effects noted were those of a macroscopic nature in general, that is cellular and sub-cellular damage
is not generally provided. An exception to this is in some mutation test where DNA damage is determined in a
number of different ways. Since the data and descriptors are essentially similar to those in RTECS no
description is provided here. It should be noted that if no references are found for a category of toxic effect,
such as a teratogen, it is not listed in the tables.
As indicated in the reference tables, the data for the compounds is often sparse. When available there is often
conflicting results in the dose levels required to provide a toxic effects. As each reference may cite procedures
which vary somewhat for the same toxic and compound, this is not necessarily surprising. It has been known for
instance that impurities in compounds have produced false positive effects with regard to toxic effects. Many
articles do not cite the proof of purity as is routinely carried out in the National Toxicity Program. Therefore,
it is always wise to use caution when evaluating dose levels provided in the appendices as no statement as to
its quality is given. For the data provided, however, it does appear in general that the levels at which any toxic
effects occur are at relatively high levels (e.g. ~1 g/kg). This provides some confidence in the safety of the
compounds used in the consumer products, but by no means have all of the results been tallied for negative
effects leaving open the question of at what point toxic effects occur in humans.
TABLE 6-1. COMPOUNDS TENTATIVELY IDENTIFIED BY GC/HRMS
AS PART OF INITIAL SCREENING
| Consumer Product |
Compounds Identified |
High Resolution Mass Spectra |
| Giorgio cologne for men |
benzaldehyde |
- |
| |
acetophenone |
+ |
| Chantilly spray mist cologne |
Beta-myrcene |
- |
| |
linalool |
+ (fragment) |
| |
limonene |
+ |
| |
Alpha-terpineol |
+ (fragment) |
| Giorgio perfume |
myrcene |
- |
| |
benzyl acetate |
- |
| Aqua Net hairspray |
none |
- |
| Coast soap |
Alpha-pinene |
+ |
| |
Beta-pinene |
+ (fragment) |
| |
limonene |
+ (fragment) |
| Renuzit Freshell air freshner |
limonene |
+ |
| Downey fabric softener |
benzyl acetate |
- |
| Sure solid deodorant / antiperspirant |
3 silane compounds |
- |
| Vaseline Intensive Care lotion |
unknown |
- |
| Max Factor nail enamel remover |
none |
- |
TABLE 6-2. FREQUENCY AND LEVEL OF INITIALLY IDENTIFIED
COMPOUNDS IN THE 31 CONSUMER PRODUCTS
Retention No. of
time Frequency Average Level Products as
(min) Compound in Products When in Product a Major Peak b
1.38 C02 1 1
6.96 vinylidene chloride 1 1
7.14 carbon disulfide 1 1
7.17 ethanol 23 1 2
7.50 acetone 11 1
8.49 methyl acetate 3 1
8.5 isopropanol 4 1
8.55 methylene chloride 7 1
9.48 tert-butanol 5 1
10.20 1,1-dichloroethane 1 1
11.04 2-butanol 4 1
11.16 1,2-epoxybutane 1 1
11.37 1-propanol 2 1
11.76 nitromethane 1 1
12.27 ethyl acetate 12 1
12.53 trimethylsilanol 1 1
12.60 1,1,1-trichloroethane 2 1
13.56 methyl isopropyl ketone 1 1
13.77 1,2-dichloroethane 1 4
15.45 trichloroethylene 1 4 1
15.87 1-butanol 1 1
16.23 1,4-dioxane 2 2
16.56 bromodichloromethane 1 1
17.40 acetic acid 3 1
18.25 toluene 4 2 1
19.92 hexamethyicyclotrisiloxane 3 2 1
22.32 ethylbenzene 2 1
22.74 di-n-butyl ether 1 1
23.19 propylene glycol 1 1
23.85 styrene 1 3
24.27 allyl isothiocyanate 1 2
24.36 2-heptanone 1 1
24.39 Beta-phellandrene a:l, b:2 1
24.66 Alpha-pinene 12 1
25.14 isopent-2-enyl acetate 1 1
25.62 camphene 5 1
26.13 3-octanone 1 1
26.83 Beta-pinene 6 1.5
26.85 Beta-myrcene 17 1
27.51 benzaldehyde 14 1
27.54 1-phellandrene 3 1
27.99 6-methylhept-5-en-one 2 1.5
28.14 2-octanone 1 1
28.00 Alpha-terpinene 6 1
28.35 limonene 23 3
28.83 1,8-cineole 10 2
28.98 4-methylanisole 4 1
29.07 3,7-dimethyl-1,3,7-
octatriene 13 1
29.50 y-terpiene 10 1
29.70 2-ethyl-1 -hexanone 1 1
29.76 diethyleneglycolmonoethyl 5 1
ether
30.39 n-undecane 2 1
30.42 Alpha-terpinolene 10 1
30.78 phenylacetaidehyde 5 1
30.90 o-altyftoluene 1 1
31.16 benzyl alcohol 14 1
31.77 3,7-dimethyl-3-octanol 5 1
31.83 rose oxide 2 1
31.95 methyl benzonate 1 1
32.00 linalool 21 3 5
33.00 7,8-dihydrolinalool 1 1
33.48 citronellal 4 1
33.60 Beta-phenethyl alcohol 20 2
33.65 n-dodecane 1 1
34.08 4-isopropylcyclohexanol 1 1
34.11 camphor 8 2
34.17 isomenthone 2 1
34.23 benzyl acetate 15 2
34.47 isoborneol 1 1
34.59 dimethyl benzyl carbinol 1 2
34.76 menthone 2 1
34.62 terpinen-4-ol 4 1
34.62 benzaldazine 2 1
34.80 menthol 1 4
34.89 bomeol 3 1
35.00 1-phenylethyl acetate 3 2
35.20 estragole 3 2
35.25 Alpha-terpineol 14 2
35.76 fenchyl acetate 2 1
35.88 2,2-dimethoxy-1-
phenylethane 2 1
36.26 Beta-citronellol 12 2
36.63 myrcenyl acetate 4 2
37.11 4-tert-butylcyclohexanone 1 1
37.17 neral 1 1
37.20 beta-phenethyl acetate 1 1
37.23 nerol 9 1
37.23 benzyl propionate 1 2
37.92 1-menthyl acetate 1 2
38.07 endobornyl acetate 1 2
38.10 1-methoxy-4- 1 1
(1 -propenyl)benzene
38.10 terpinyl acetate 2 2.5
39.09 p-diacetylbenzene 1 1
39.48 citronellyl acetate 1 1
39.58 Beta-terpinyl acetate 2 1
40.02 Alpha-copaene 5 1
40.66 piperonal 1 1
40.81 eugenol 3 1
41.31 Alpha-cedrene 3 1
41.77 Alpha-guaiene 2 2.5
44.02 My-methyl ionone 5 1
44.22 2,6-di-tert-butyl-4- 3 1
methylphenol
a Levels are relative to largest peak by TIC (total ion current).
1 = 0 - 25 %ile
2 = 25 - 50 %ile
3 = 51 - 75 %ile
b 4 = 76 - 100 %ile
Major peak meaning the largest peak by TIC. No data indicates not
a major peak in any product.
TABLE 6-3. POLAR COMPOUNDS USED IN STANDARDS
FOR ANALYSIS OF HEADSPACE SAMPLES
Mixture Compound CAS Registry No.a
A ethanol 64-17-5
methyl acetate 79-20-9
2-butanol 78-92-2
1,1,1-trichloroethane 71-55-6
2-heptanone 110-43-0
beta-pinene 127-91-3
2-octanone 111-13-7
cineole 470-82-6
3,7-dimethyl-3-octanol 78-69-3
benzaldazine 588-68-1
Alpha-terpineol 98-55-5
bomyl acetate 76-49-3
B acetone 67-64-1
methylene chloride 75-09-2
1-propanol 71-23-8
myrcene 123-35-3
limonene 138-86-3
n-undecane 1120-21-4
benzyl alcohol 100-51-6
citronellal 106-23-0
benzyl acetate 140-11-4
1-phenethyl acetate 103-45-7
menthyl acetate 89-48-5
Alpha-terpinyl acetate 80-26-2
Beta-methyl ionone 127-51-5
c isopropanol 67-63-0
acetic acid 64-19-7
camphene 79-92-5
benzaldehyde 100-52-7
2-ethyl-l-hexanol 104-76-7
B-phenethyl alcohol 60-12-8
terpinen-4-ol 20126-76-5 b
4-allylanisole (also estragole) 140-67-0
fenchyl acetate unknown c
Beta-citronellol 106-22-9
Alpha-cedrene 469-61-4
D t-butanol 75-65-0
ethyl acetate 141-78-6
methyl isopropyl ketone 563-80-4
toluene 108-88-3
Alpha-pinene 80-56-8
3-octanone 106-68-3
diethylene glycol monoethyl ether 111-90-0
phenylacetaldehyde 122-78-1
linalool 78-70-6
camphor 76-22-2
citral 5392-40-5a
nerol 106-24-1
1,4-diacetylbenzene 1009-61-6
2,6-di-t-butyl-4-methylphenol 128-37-0
a Is CAS R.N. for compound with unspecified optical activity in
cases where optically active forms are possible.
b Is the RN for (R)-(-) form. General RN was not found.
c No RN was found for this compound.
d Includes E and Z forms.
TABLE 6-4. HEADSPACE GENERATION AND COLLECTION PARAMETERS USED
FOR THE 5 SELECTED CONSUMER PRODUCTS
Amount of Collection Collected
Product, level loaded Product Used a Time (min) Volume (mL)
Blanks -- 5.0 500
Giorgio cologne, low 10 uL 2.5 250
Giorgio cologne, high 20 uL 3.75 375
Chantilly cologne, low 10 uL 2.5 250
Chantilly cologne, high 20 uL 3.75 375
Giorgio perfume, low 10 uL 2.5 250
Giorgio perfume, high 20 uL 3.75 375
Coast soap, low 2.5 g 2.50 250
Coast soap, high 5 g 3.75 375
Renuzit Air Freshener, low 5 drops 2.5 250
Renuzit Air Freshener, high 10 drops 3.75 375
a The amount of product put into the headspace jar.
TABLE 6-5. COMPOUNDS IDENTIFIED IN THE
HEADSPACE OF GIORGIO COLOGNE FOR MEN
Standard R.T. (min) High Resolution Mass Spectral Data a
Peak or Mass to Change Ratios Parent Ion Theoretical ppm
Compounds No. Unknown GC/MS GC/HRMS (Relative Intensities) (Rel. Irt.) m/z deviation Formula
Beta-pinene 3 41 69 77 79 91 93 94 121 136
std 20.77 18.35 (12) (22) (20) (20) (28) (100) (13) (14) (12) 136.1252006 -10.8 ClOH16
unk 20.73 18.33 (47) (45) (22) (22) (28) (100) (13) (10) (9) 121.1017255 10.7 C9Hl3
Beta-myrcene 4 41 67 69 77 79 91 92 93 136
std 21.34 19.07 (33) (10) (58) (14) (16) (25) (12) (100) (5) 136.1252006 1.1 ClOH16
unk 21.32 18.97 (86) (13) (90) (14) (15) (20) (11) (100) (4) 93.04259327 27.8 C2H7NO3
linalool 10 39 41 43 55 67 71 93 121 154
std 27.26 25.25 (39) (75) (100) (57) (29) (65) (93) (43) (1) 136.1252006 -0.7 ClOH16
unk 27.21 25.25 (20) (60) (58) (56) (19) (100) (58) (11) (ND)b 121.1017255 2.4 C9Hl3
Beta-phenethyl
alcohol 12 51 65 77 78 91 92 93 122 122
std 29.10 27.25 (10) (23) (9) (7) (100) (84) (9) (59) (59) 122.0731650 -1.7 C8H10O
unk 29.07 27.40 (8) (19) (5) (4) (100) (58) (4) (26) (26) 122.0731650 -0.2 C8H10O
benzyl acetate 13 77 79 89 90 91 107 108 150 150
std 29.93 27.97 (14) (23) (15) (33) (51) (18) (100) (40) (40) 150.0680797 -24.6 C9H10O2
unk 29.91 28.10 (ND) (28) (19) (44) (60) (18) (100) (25) (25) 150.0680797 29.7 C9H10O2
ethanol 1 40 41 42 43 44 45 46 47 46
std 2.57 c (2) (4) (10) (24) (5) (100) (45) (2) (45) 46.0418469
unk 2.17 2.97 (<1) (1) (3) (4) (ND) (100) (45) (2) (45) 46.0418649 2.1 C2H6O limonene 67 68 79 93 94 107 121 136 136 std 23.05 (78) (84) (49) (100) (42) (36) (41) (45) (45) unk 20.77 (63) (100) (37) (92) (39) (35) (42) (50) (50) 121.1017255 5.6 C9Hl3 estragole (or 91 105 115 117 121 133 147 148 148 4-allylanisole std. 30.85 (22) (22) (21) (34) (32) (22) (63) (100) (100) unk 28.75 (23) (5) (2) (8) (18) (3) (8) (24) (24) 148.0888151 7.2 ClOH12O Beta-citronellol 17 67 69 81 82 95 109 123 138 156 std 32.33 30.62 (75) (100) (97) (80) (92) (42) (56) (37) (22) 138.1408507 8.6 ClOH18 unk 32.30 30.55 (46) (100) (42) (43) (26) (12) (12) (7) (5) 82.0275420d no match Alpha-pinene 2 77 79 91 92 93 105 121 136 136 std 18.62 16.18 (27) (22) (46) (38) (100) (13) (14) (13) (13) 121.1017255 1.4 C9H13 unk 18.59 (26) (18) (40) (35) (100) (8) (9) (10) (10) benzaldehyde 5 50 51 74 77 78 105 106 107 106 std 22.00 19.90 (3) (7) (5) (53) (10) (100) (98) (8) (98) 106.0418649 21.1 C7H6O unk 21.99 (26) (48) (8) (100) (14) (90) (97) (8) (97) phenylacetaldehyde 8 39 51 63 65 89 91 92 120 120 std 25.75 23.50 (4) (3) (4) (14) (4) (100) (23) (24) (24) 120.0575150 0.0 C8H8O unk 25.78 (10) (6) (8) (19) (4) (100) (21) (20) (20) 3,7-dimethyl-1,3,7- octatriene 6 39 41 77 79 00 91 92 93 136 unk 23.81 21.65 (28) (37) (37) (48) (42) (50) (24) (100) (8) 121.1017255 14.8 C9H13 noxylethane 9 41 43 55 59 67 69 70 83 158 unk 26.17 24.27 (12) (17) (16) (100) (9) (7) (7) (7) (ND) 108.0575150 13.7 C7H8O neryl acetate 51 68 69 70 84 93 121 123 196 unk 31.53 (6) (18) (100) (7) (6) (25) (6) (12) 136.1252006 3.8 C10H16 Alpha-copaene 18 41 91 93 105 119 161 189 204 204 unk 36.64 34.73 (52) (47) (55) (62) (85) (100) (98) (45) (45) 204.1878010 4.5 C15H24 y-methyl Ionone 19 41 43 79 91 107 123 135 150 206 unk 41.06 39.50 (20) (53) (12) (30) (67) (18) (100) (63) (9) 150.1044652 12.9 C10H14O y-terpinene 7 43 77 79 91 92 93 121 136 136 unk 24.21 (25) (37) (21) (53) (23) (100) (24) (34) (34) alloocimene 11 41 43 56 79 91 105 121 136 136 unk 27.90 (48) (38) (36) (39) (28) (44) (100) (46) (46) unknown 15 77 91 115 117 121 133 147 148 unk 30.76 (27) (20) (22) (31) (39) (19) (60) (100) ClOH12O 16 39 43 55 65 91 119 120 134 148 unk 31.31 (13) (12) (11) (23) (75) (100) (12) (76) (2) benzolc acid 14 50 51 77 78 105 106 122 150 122 unk 30.04 28.10 (6) (19) (44) (4) (100) (8) (27) (16) (27) a High resolution data is provided when avalable. b ND="not" detected. C Retention time was not available from one instrument due to unclear spectrum or not being detected. d Actual m/z measured since no match within ±30 ppm was found.
TABLE 6-6. COMPOUNDS IDENTIFIED IN THE
HEADSPACE OF
CHANTILLY SPRAY MIST COLOGNE
(only compounds are listed, for full table with mass-to-change rations, etc,
see original report)
- Beta-myrcene
- benzyl alchohol
- linalool
- camphor
- ethanol
- limonene
- toluene
- Alpha-pinene
- camphene
- benzaldehyde
- 1,8-cineole
- benzyl acetate
- terpinen-4-ol
- Alpha-terpinol
- 3,7-demethyl-1,3,7-octatriene
- neryl acetate
- Gamma-methyl ionene
- acetaldehyde
- 2-methyl-2-butenal
- ethylbenzene
- Alpha-terpinolene
- acetophenone
- mentha-1,4,8-triene
- borneol
- dimethylstyrene isomer
- C15 H24
- C15 H26
- C10 H16
TABLE 6-7. COMPOUNDS IDENTIFIED IN THE
HEADSPACE OF GIORGIO PERFUME
(only compounds are listed, for full table with mass-to-change rations, etc,
see original report)
- Beta-pinene
- benzaldehyde
- benzyl alcohol
- linalool
- benzyl acetate
- Alpha-terpineol
- Beta-citronellol
- ethanol
- limonene
- Beta-phenethyl alcohol
- Beta-myrcene
- Alpha-cedrene
- t-butanol
- ethyl acetate
- toluene
- camphene
- 2-ethyl-1-hexanol
- 3,7-dimethyl-1,3,7-octatriene
- C15 H24
- crotonaldehyde
- 2-furaldehyde
- Gamma-terpinolene
- Alpha-terpinolene
- phenyl acetaldehyde
- o-allytoluene
- acetophenone
- alloocimene
- 2-methyl-4-phenyl-1-butene
- carvone
TABLE 6-8. COMPOUNDS IDENTIFIED IN THE
HEADSPACE OF COAST SOAP
(only compounds are listed, for full table with mass-to-change rations, etc,
see original report)
- Alphe-pinene
- camphene
- Beta-pinene
- benzyl alcohol
- linalool
- citronellal
- benzyl acetate
- 1-methyl acetate (isomer)
- limonene
- 3-octanone
- ethanol + acetone
- toluene
- 2-methyl-2-propenal
- n-heptane
- n-propyl acetate
- C10 H18
- C12 H20 O2 (acetate)
- C12 H20 O2 (ester)
TABLE 6-9. COMPOUNDS IDENTIFIED IN THE
HEADSPACE OF
RENUZIT FRESHELL AIR FRESHENER
(only compounds are listed, for full table with mass-to-change rations, etc,
see original report)
- camphene
- beta-pinene
- diethylene glycol monoethyl ether
- linalool
- Beta-phenethyl alcohol
- camphor
- limonene
- benzaldehyde
- ethyl acetate
- Beta-myrcene
- 1,8-cineole
- C10 H18 + Alpha-pinene
- ethanol
- 1-phenethyl acetate
- 3-methyl-2-pentanone
- Carvone
- 2-t-butylcyclohexanol
- alcohol
- ester
- C10 H18 O
- unknown
Figures 6-1 to 6-6 omitted.
Tables 6-10 to 6-14 omitted
TABLE 6-15. LITERATURE SEARCH PROCEDURE
AND NUMBER OF CITATIONS RESULTING
No citations No Citations selcted
Search Procedure a retrieved in search for Retrieval
CancerLit/ CancerLit/ CancerLit/
Compound ToxLine CAS ToxLine CAS ToxLine CAS
ethanol b - - - - - -
camphene 1 5 127 21 8 1
Beta-pinene 1 5 41 1
myrcene 1 5 56 33 2 4
benzaldehyde 2 5(1st 100)+2 91 121 8 1
limonene 1 5 224 77 3 17
benzyl alcohol 2 5 83 118 0 19
beta-phenethyl
alcohol 1 5 69 23 20 2
citronellal 1 5 103 46 1 0
camphor 1 5 309 50 30 0
benzyl acetate 1 5 91 24 15 5
estragole 1 5 151 16 10 1
Alpha-cedrene 1 1 8 41 2 1
Alpha-pinene 1 10+6 164 92 14 10
diethylene glycol
monoethylether 1 5 93 30 7 0
linalool 1 5 111 45 14 3
Alpha-terpineol 1 5 61 35 6 2
beta-citronellol 1 5 9 1 0 0
menthyl acetate 1 5 9 1 0 0
acetone 3 5 + 3 203 122 9 3
t-butanol 1 5 239 111 19 1
3-octanone 1 5 16 13 3 2
cineole 1 5 60 17 8 0
phenacetaidehyde 1 5 44 35 9 0
a Following are the codes for the search procedures used. Note English
(or unspecified) only is assumed. For Keywords '?" implies a suffix of
0 or more characters. The operators "and" and "or' are logical operators.
1: all references (CAS references are not in ToxLine or CancerLft)
2: Keyword is "human".
3: Keywords: "human" and ("skin?' or ("breath?" or "inhal?" or "lung?")).
4: Keywords: "mutagen?' or 'carc?" or "teratogen?" or "irfit,?'.
5:Keywords: from #4 or "toxic?".
6:Keywords: "mutagen?" or 'carc?' or 'teratogen?".
7:Keyword: 'mutagen?'
8:Keyword: "carc?'
9: Keyword: 'teratogen?'.
10: Keyword: 'toxic?'.
b Not retrieved as number of references was too large.
Tables 6-16 to 6-39 omitted.
Section 7, References, containign 370 references, omitted.
See the complete report for these tables and references.
APPENDIX B
REFERENCES FOR
TOXICOLOGICAL PROPERTIES OF FRAGRANCE COMPOUNDS
REFERENCES FOR TOXICOLOGICAL PROPERTIES OF IDENTIFIED COMPOUNDS
--------------------------------------------------------------------------------------------------------
Compound Animal Carcinogen Mutagen Eye Irritation Skin Irritation Teratogen Other toxic
Type a Effects b
--------------------------------------------------------------------------------------------------------
ethanol human __c 37,40-41,47 -- -- 53-54,80,85 12-17,23
rodent 32-33 37,42-36, 55-68,77,79, 9-11,18-19,21
48-49,52 -- -- 81,86-96 25-26,28,30-31
other 5-8 34-36,38-39, 6-8 5-6 69-76,78, 15,20,22,24,
50 82-84,94 27-30
camphene rodent -- 97 -- -- -- --
Beta-pinene rodent -- -- -- -- -- 98
other -- -- -- 98 -- --
myrcene rodent -- -- -- -- -- 99-100
other -- -- -- 99 -- 99
benzaldehyde
human -- 108 -- -- -- --
rodent 105,107 105,109-110 -- -- -- 101-104
other 106 -- -- 101 -- 102
limonene rodent 117-124 -- -- -- 125-128 113-116
other -- -- -- 111-112 129-130 --
benzyl alcohol
all -- -- -- -- -- --
Beta-phenethyl
alcohol
human -- -- 131 132-134 -- --
rodent -- 156 -- 132,138 151-154 139-148,150
other -- 159 -- -- -- --
citronellal
rodent -- 159 -- -- -- --
other -- 159 -- 158 160
camphor human -- -- -- 161 -- 162-167
rodent 177-179 180 -- -- -- 162,168,170-176
other -- -- -- 161 162-169
benzyl acetate
human -- 194 -- -- -- 182
rodent 189-192 194-195 -- -- -- 182
other -- 193 -- 181 -- 183-184, 18
estragole rodent 199-203 205-206 -- -- -- 196-198
other -- 204 -- 196 -- --
Alpha-cedrene
other -- -- -- 207 -- --
Alpha-pinene
human -- -- 212 209-211 -- --
rodent -- -- -- 208 -- --
other -- 213-214 -- 210 -- --
diethylene glycol monoethyl ether
rodent 218, 223 -- -- -- 219,236-238 218-221,223-226
228-235
other -- 230 216-217 215 -- 221-222,224
227-228,231
linalool human -- -- -- 239,242 -- --
rodent 248 -- -- 239 -- 243-247
other -- 249-251 -- 239-241 -- 240
Alpha-terpineol
human -- -- -- 252 -- --
rodent 257 -- -- -- -- 254-256
other -- 258 -- -- -- 253
Beta-citronellol
human -- -- -- 259 -- --
rodent -- -- -- 259 -- 260-262
other -- -- -- 259 -- 260
--------------------------------------------------------------------------------------------------------
a Rodent includes rats, mice, guinea pigs and hamsters. Other includes
rabbits, cats, dogs and miscellaneous.
b Other toxic effects such as behavioral abnormalities and death.
c No data for an effect (positive or negative) was found.
REFERENCES FOR TOXICOLOGICAL PROPERTIES OF COMPOUNDS TENTATIVELY IDENTIFIED
--------------------------------------------------------------------------------------------------------
Compound Animal Carcinogen Mutagen Eye Irritation Skin Irritation Teratogen Other toxic
Type a Effects b
--------------------------------------------------------------------------------------------------------
acetone human --c -- 364 -- 309,311 264-265,270-273
276-277
rodent 286-206 307 -- -- 310 274-275,278-280,
282-283,285
other 304 308-309 265-266, 267-268 311 265,280-281,
268-269 284
t-butanol rodent 320-321 325-326 -- -- 313,328-332 312-314,316-318
other -- 322-324,327 -- -- -- 315,319
ethyl acetate
human -- -- 333 334 -- 333
rodent 349-351 352,356 -- -- -- 335-339, 341,
343-348
other -- 352-354 -- -- -- 335-339, 341,
343-348
other -- 352-354 -- -- -- 340,342,348
3-octanone rodent -- -- -- -- -- 357
other -- -- -- 356 -- --
cineole rodent 363-364 365 -- -- -- 358-362
other -- -- -- -- -- 358
phenylacetaldehyde
human -- -- -- 366-368 -- --
rodent -- -- -- -- -- 369-370
other -- -- -- -- -- 370
menthyl acetate
rodent -- -- -- -- -- 263
other -- -- -- 263 -- 263
--------------------------------------------------------------------------------------------------------
a Rodent includes rats, mice, guinea pigs and hamsters. Other includes
rabbits, cats, dogs and miscellaneous.
b Other toxic effects such as behavioral abnormalities and death.
C No data for an effect (positive or negative) was found.
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3. 
3.2. EPA Study