new the sampling and identification of components in volatile … · 2014. 11. 25. · techniques...
Post on 11-Oct-2020
0 Views
Preview:
TRANSCRIPT
THE SAMPLING AND IDENTIFICATION OF COMPONENTS
IN VOLATILE ORGANIC MIXTURES
by
R.B. Chesterman, Utp. App. Chem.
Submitted in partial fulfilment
of the requirements for the degree of
Master of Science
UNIVERSITY OF TASMANIA
HOBART
December 1982 cp-A-ce_rect. Maid— (183)
Except as stated therein, this thesis
contains no material which has been accepted
for the award of any other degree or diploma
in any university, and that, to the best of my knowledge
and belief, the thesis contains no copy or paraphrase
of material previously published or written by another
person, except when due reference is made in the text.
R. B. Chesterman
ACKNOWLEDGEMENTS
I wish to gratefully acknowledge the advice and
encouragement of my supervisors, Professor H. Bloom,
Dr. B.V. O'Grady, and Dr. I.R.C. Bick, who offered many
helpful suggestions during the course of this work.
I am also indebted to Mr. C. Richards of the Chemistry
Department workshop for the construction of the prototypes
of - the sample desorption equipment; and to Mrs. H. Hen,
Mrs. B. Dix and Mrs. B. Thompson of the secretarial staff
who assisted with the preparation of the diagrams and
figures, and who answered once again with patience,
questions concerning preparation of the text that must
have been put to them many hundreds of times before.
The assistance of the staff of the Central Science
Laboratory for help with mass spectral and information
processing of material is gratefully acknowledged.
The help of Dr. J. Madden, and the staff of the CSIRO
Forest Research Section at Cambridge, for logistic and
other support is .. gratefullyacknowledged. For the help of
my wife Lynne with the typing, and her understanding of the
curtailment of family life associated with part-time
studies I will be always grateful.
CONTENTS
Page No.
CHAPTER I INTRODUCTION. 1
CHAPTER II EXPERIMENTAL TECHNIQUES FOR THE CONCENTRATION AND ANALYSIS OF VOLATILE ORGANIC COMPOUNDS. 2 A.Concentration and Trapping Techniques. 3 B.Direct Headspace Collection. 15 C.Separation and Analytical Techniques. 17 • D.Detection and Analytical Techniques. 25 E.Sources of Error in Trace Volatile
Analysis. 29
CHAPTER III DEVELOPMENT OF A SAMPLING SYSTEM FOR VOLATILE ORGANIC MIXTURES. 32 A.Selection of a Sample Adsorption Medium. 34 B.Development of Sample Collection
and Desorption Equipment. 40 C.Blank Determinations and Sample
Trap Storage. 47
CHAPTER IV AN EXPERIMENTAL COMPARISON OF VOLATILE ORGANIC SAMPLING TECHNIQUES. 54 A.Experimental. 55 B.Discussion. 66 C.Summary and Conclusions. 69
CHAPTER V VOLATILE COMPONENTS OF SOME NATIVE PLANTS. 70 A.Components of the Steam Volatile Oil
of Drimys lanceolata. 71 B.Components of the Steam Volatile Oil
of Prostanthera lasianthos 83 C.Volatile Components of
Boronia megastigma 94
CHAPTER VI VOLATILE COMPONENTS OF PINUS RADIATA. 102 A. The Composition of the Steam Volatile
Components of Bark Oil P. radiata 106 B. Collection of Headspace Samples From
the Bark of P. radiata. 110 C. A Comparison of Bark Volatiles From
a Girdled P. radiata 113 D. Composition Changes of Bark Headspace
of P. radiata. 122
CHAPTER VII CONCLUSIONS
126
REFERENCES
129
APPENDIX
143
ABSTRACT
Public awareness of the toxic effects of some volatile
organic compounds present in the working and home
environment has created a requirement for the accurate
measurement of the concentration of these substances.
Similar techniques may be used for the examination of the
volatile components of plant material and assist in
determining the optimum economic time for harvesting, and
also provide useful information in the areas of plant-insect
interaction. This thesis examines some of the sampling and
analytical aspects for the determination of trace volatile
organic compounds present in air.
A brief critical review of the literature is presented
describing concentration and trapping techniques, headspace
collection, separation and analytical techniques, detection
and measurement of the separated components and the sources
of error in trace volatile analysis.
The development of an experimental sampling system for
volatile organic compounds in air, based on trials conducted
with activated carbon and a porous polymer is presented.
• Two methods of sample desorption are described and the
development of sampling equipment based on Tenax GC, thermal
elution with secondary trapping and flash injection into the
inlet of a gas chromatograph is described.
An investigation was conducted into the nature and
origin of an unpleasant lachrimatory component emanating
iv
from an industrial furnace, and a number of trapping and
separation techniques were used to determine the nature of
the irritant. The experimental methods used are described,
and conclusions are drawn concerning the suitability of the
various techniques for trace organic volatile sampling.
The steam volatile components of the oil of two
Tasmanian native plants, Drimys lanceolata and Prostanthera
lasianthos are examined using gas chromatography retention
criteria on two columns and mass spectral information. A
comparison of the volatile components of Boronia megastigma
in the flowers, concrete, and.concrete headspace is
described and the application of the technique to the
determination of the optimum time for harvesting, is
outlined.
Changes in the volatile components produced upon injury
of Pinus radiata are examined using headspace traps above
and below the injury and comparisons are made of the
volatile components present in the bark.
ABBREVIATIONS
GC - Gas Chromatograph
FID - Flame Ionisation Detector
MS - Mass Spectrometer
TIC - Total Ion Current
HPLC - High Performance Liquid Chromatography
CW2OM - Carbowax 20M Stationary Phase
OV101 - OV Silicone 101 Stationary Phase
GLT - Glass Lined Stainless Steel Tubing
SCOT - Support Coated Open Tubular (Column)
WCOT - Wall Coated Open Tubular (Column)
MIKES - Mass-analysed Ion Kinetic Energy Spectrometer
PMD - Programmed Multiple Development (Chromatography)
TDL - Toxic Dose Level
ppb - Part per billion
ppm - Part per million
Deg.C-Degrees Celsius
1
INTRODUCTION
The identification of components in complex mixtures of
volatile organic substances, plant volatiles, working and
living atmospheres, and volatile substances of forensic
interest, has been limited by the techniques available for
collection and identification.
Identification of compounds in some workday situations
has established the presence of a number of carcinogenic,
mutagenic and teratogenic agents as well as those known to
cause liver and other vital organ malfunctions. An
increasing awareness of the influence of some volatile
components on human health has created the need for a
generally acceptable group of techniques for their
separation and identification.
Major problems associated with the investigation of
volatile components include the degree of uncertainty of
identification due to formation of rearrangement products
and artefacts, and to laboratory contamination. Volatile
organic materials present in the atmosphere of work places,
industrial areas, hospital operating theatres, city streets,
waste chemical dumps all present some degree of hazard to
human well-being. This thesis examines the concentration,
separation and identification-of some volatile organic
mixtures present in a number of distinct but related areas.
2
CHAPTER II
EXPERIMENTAL TECHNIQUES FOR THE CONCENTRATION AND ANALYSIS
OF VOLATILE ORGANIC COMPOUNDS.
Introduction
The sampling of volatile organic materials in a variety
of atmospheres ranging from the confined air in a space
capsule [1] to background levels in isolated geographical
regions of the earth's surface requires collection,
concentration and identification techniques with varying
degrees of complexity.
Individual component monitoring and identification is
essential in an enclosed area, such as an industrial site,
where the need to recognise the health hazard that specific
compounds have for persons continually exposed to volatile
organic materials. The tracing, fingerprinting and
identification of odorous volatile components in other areas
such as processing plants, sewage treatment works and
abattoirs would also provide information on the degree of
risk of exposed persons to hazardous compounds. The
qualitative and quantitative trapping and identification of
components would provide some scientific basis for the
measurement of odours and some other parameters affecting
what is loosely termed "the quality of life" in an
increasingly more crowded environment.
3
A. Concentration and Trapping Techniques
Techniques for the sampling of volatile organic mixtures
in the atmosphere necessitate the concentration of
components to a point where separation and measurement is
within the capabilities of the analytical instrumentation.
The concentration of components by factors of one hundred to .
ten thousand are often required.
Trapping or concentration techniques may be considered
under three major headings: condensation methods,
adsorption methods and headspace techniques.
(i) Condensation or Cryogenic Methods
Earlier attempts to concentrate volatile organic
materials from air involved the passage of litre quantities
of air through a stainless steel or glass U-tube immersed in
a freezing mixture of solid carbon dioxide/acetone, or
liquid nitrogen [3 -5]. Volatiles and semi- volatile
components of cigarette smoke [6] and food products [7] have
been trapped utilising this technique. Detection limits of
2 ,ug/m have been claimed [8]. In 1967 Willis [9]
described a trapping system involving the cryogenic
collection of a sample in one loop of a gas chromatograph
(GC) separating column. Improved resolution was claimed
especially for lOw molecular weight (Cl to C5) hydrocarbons.
However, as a rapid routine method of sample trapping there
are obvious practical limitations; for example the carriage
of cryogenic liquids to remote or awkward situations (such
as the inside holds of ships) [8].
Baker in a series of articles [10,11], summarised and
reviewed some earlier theoretical and practical aspects of
trace organic contaminant concentration by freezing. A
major problem associated with cryogenic trapping procedures
is the co-condensation of considerable quantities of water
and the inherent losses of low molecular weight water
soluble compounds upon its removal. Tyson and Carle [12],
circumvented this by passing the cryogenically trapped
water-organic mixture through a preparative GC to separate
the water and then through a gas chromatograph/mass
spectrometer (GC/MS) for identification of components
(Figure 1). High recovery efficiencies were obtained for a
selection of terpenes.
Pa" MPAROME 001051
1412 ir eh ! m 0(110101
511000
FLOW
SECOND S ACE SEW 550,11
VENT Two AA? I r I 1i?001000
UOVTICAL 00550100VENT
0 (:—:11 1110F1 2.51111.1 ,(4 M AUER. FLUE
SUM I 1 qu
TOlassoC4 I 1:11/ATIOI VASS
RAP , f
SW f sw MU 01110100 SPECTOONETEI
NEM
SAMPLE IN
FIAST SEW IRA?
CRYOGENIC PRECONCENTRATOR
PREPARATIVE GAS CHROMATOGRAPH
GC—MS
Figure I. Schematic Diagram of a Preconcentration and Analytical System [12].
Cryogenic trapping in conjunction with hydrophobic
porous polymers is an effective method for sampling low
boiling point organic compounds such as ethylene [15].
Teranishi [13] utilised cryogenic trapping procedures for
collection of volatile metabolites from human breath and
^
5
urine; and Copier [14] trapped eluent from a GC on cooled
glass tubes for subsequent IR analysis.
(ii) Adsorption Methods
(a) Carbon Trapping
Carbon in various forms has been widely used for
collecting organic compounds from air [16,17] and water
[18,19]. Activated carbon has differing adsorption
properties depending upon its source material (coconut,
bone, coal or wood), and its particle size. The use of
activated carbon for the economic removal of trace organic
compounds from water has been of increasing importance
following legislation introduced by the U.S. Environmental
Protection Authority, brought about by the discovery of
carcinogenic compounds in New Orleans water [20]. Volatile
halogenated hydrocarbon concentrations have been limited by
U.S. legislation to 0.5 pg/L.
Small quantities (25mg) of carbon have been used by Grob
and Grob [21] to trap microquantities of organic material
from the air. However, with small absorbent weights, air
flow rates need to be low ca. 2.5 mL/min, and sampling
times, as a result, have to be extended to allow collection
of sufficient weight of sample. A wide range of molecular
weight compounds have been collected and analysed by this
method, despite some comment [22], that catalytic changes
and irreversilbe absorption of higher molecular weight
compounds may occur.
6
Desorption of trapped components from activated charcoal
has been effected by vacuum [23] and steam [24], but the
most efficient method appears to be solvent extraction
[25,21,26], using dichloromethane or carbon disulphide.
Rubenstein [27] covers some of the theoretical aspects
of sorption using activated carbon as an example.
b) Coated Support Trapping
The equilibrium concentration of trace organic compounds
upon a liquid stationary phase has been utilised by a number
of authors [32,33], for collection of volatiles from air,
and other gases, to enable subsequent identification and
quantitation by GC. Quantitative trapping of small
quantities of organic components at ambient temperatures on
a support bonded silicon phases has been described in an
excellent paper by Aue [34]. The elution method described
involved reflux solvent extraction and concentration of
solvent before injection into the GC. Loss of volatile
fractions is likely to occur as a result of this latter step
and this problem is mentioned in the paper. Another
difficulty likely to be encountered with the use of support
bonded coatings and solvent extraction techniques is the
possible removal of very minute quantities of coating and,
the degradation of labile components under warm solvent
reflux conditions. Bellar et al [35] described an earlier
sample trapping system using a combination of liquid phase
coated firebrick and cryogenic condensation to identify more
abundant atmospheric hydrocarbons at concentrations of 0.1
7
ppb in 300mL of air. A system of collecting and
transferring amounts as small as 10mg of substances of
varying volatilities utilising coated supports is discussed
by Bierl et al [35a]. Percentage recoveries varied from
seventy to one hundred. However, only single compounds are
mentioned and the system described would not appear to have
the versatility to trap and recover a wide range of
compounds due to the selectivity of liquid phase on the
packing material.
c) Porous Polymer Trapping
Microporous polyethylene was first used as a low
temperature support in 1963 by Baum [39]. A number of
reviews [40] and papers [41-47], have documented the more
recent developments of this packing and trapping material.
Various types of porous polymers are widely used for
separating water, alcohols and aldehydes [48] ao,s well as for
the analysis of low molecular weight gases [49,50].
Authors differ in explanations as to the mechanism of
adsorption and desorption of porous polymers when used for
trapping and elution of organic compounds. Hollis [40]
suggested that the solubility of the compound in the polymer
is the most important factor in determining the order of
elution, whereas Smith and Waddington [51] indicated that
within a class of compounds there is a linear relationship
between log retention time and boiling point of the eluent.
However, pore size distribution, micropore volume, nature of
the polymer and surface activity are all important features [52].
8
Dave [53] reviewed and summarised the information
available on porous polymers up to 1969. (Table 1).
Porous Polymer Surface Area
m 2/g
Average Pore Dia.
(Angstrom)
Water Affinity
Temperature Limit
(Isothermal) °C
Chemical ,Composit• ion
"Chromosorb" 101 30-40 3500 Hydrophobic 300 STY-DVB
"Chromosorb" 102 300-400 85 Hydrophobic 250 STY-DVB
"Chromosorb" 103 15-25 3500 Hydrophobic 250 STY-DVB
Porapak N 437 - Hydrophobic 200 -
Porapak P - - Hydrophobic 250 DVB-STY
Porapak Q 840 74.8 Hydrophobic 250 EVB-DVB
Porapak Q-S - - Hydrophobic 250
Porapak R 780 75.6 Hydrophobic 250 NVP
Porapak S 670 76.0 Hydrophobic 300 ?
Porapak T 450 91.4 Hydrophobic 200 EGMA
PAR 1 100 200 Hydrophobic 250
PAR 2 300 90 Hydrophobic 250
Tenax GC 19 720 Hydrophobic 375 DPPO
XAD-2 300 90 Moderate 200 DVB
DPPO = 2,6-diphenyl-p-phenylene oxide; STY = styrene; DVB = divinyl benzene; EVB = ethyl vinyl benzene; NVP = N-vinyl pyrrolidone; EGDMA = ethylene glycol dimethacrylate.
Table I. A Comparison of the Physical Properties of Some Porous Polymers [53].
9
The development in 1972 by Applied Science Laboratories
of a new porous polymer, 2,6-diphenyl-p-phenylene oxide
(Tenax GC) provided a versatile, efficient, thermally stable
trapping medium that has been widely used for trapping
volatiles from air [2,54,55,56], water [2,57], and
biological samples [54,58].
A number of authors have compared the various types of
porous polymers available for sample trapping and have
reached different conclusions [59], Butler and Burke [60]
after an investigation utilising test samples of t-butanol,
methyl ethyl ketone, benzene and acetonitrile, concluded
that Porapaks Q and R had the best overall sampling
capacities. However, the statement was made that Tenax GC
may be the absorbent of choice for samples consisting of
high boiling components because of the high temperature
limit.and relatively low retention volumes. These
characteristics allow sample components to be desorbed more
rapidly from Tenax than from other adsorbents.
Zlatkis et al have used Tenax GC as a trapping system
for volatiles from human breath [54], urine [54,61], and
plasma [58], but do not appear to have critically evaluated
the method for loss of volatile components. Pellizzari et al
have conducted the most systematic comparison of collection
efficiencies [62], and field sampling variables with Tenax
GC [63]. The effects of humidity, background load levels,
repeated re-use of sorbent, and transportation and storage
of collected samples were investigated. Tenix GC was
- 10-
superior to other sorbents in most cases, percentage
recovery by thermal elution procedures being better than 90%
at the 50 and 100 mg level [64].
Another porous polymer, XAD-2, has been widely evaluated
[65] and used [66-68], for the trapping of trace amounts of
organic materials mainly in water. Claims are made that the
concentration range extends from 5 parts per trillion (10 11 )
to 50 ppm [65]. It should be noted that some of the claims
made in this paper especially concerning recoveries of some
higher molecular weight acids have not been verified in this
laboratory [69]; Nevertheless, the method has found many
applications in trace organic water analysis [70, 71]
despite some of the limitations posed by the removal of
water from the organic extract and the losses entailed.
Morrison et al [70] claimed that "thermal desorption
makes quantitative analysis difficult". This view contrasts
with the opinion of a number of other authors [72 - 74], who
have successfully used Tenax GC and thermal desorption
techniques. As a result of the improvement in sample
collection efficiency and the coupling of powerful capillary
GC mass spectrometer computer systems, over one hundred
volatile components have been collected and identified from
atmospheric sources [56] using Tenax GC. Ciccioli et at
[75] compared the recoveries of Tenax GC and concluded that
a mixture of 0.25g of Tenax GC and 0.45g of Carbopac B
provided a good compromise for the trapping of most volatile
organic compounds from open air and industrial sites. (Table II)
A cryogenic trapping procedure however, was advocated
for low boiling point compounds up to the boiling point of
pentane.
Dressler has published a review of applications of
porous polymers for the extraction of trace organics from
aqueous samples [76] and commented on aspects of method
sensitivity and sample storage.
- 12 -
Compound ' tarbopack B Tenax GC
0.5 L sample
1.5 L sample
5.0 L sample
0.5 L sample
1.5 L sample
5.0 L sample
Methanol 3 0 0 1 0 0
Ethanol' 3 0 0 1 0 0
Methyl chloride 1 0 0 3 1 0
Acetone 5 1 0 68 2 0
Chloroform 100 54 1 100 84 5
Diethylamine 100 80 50 80 50 r
Isobutanol 100 100 25 100 95 16
n-Pentane _ 100 100 100 100 50 9
Cyclohexane 100 100 100 100 50 9
n-Hexane _ 100 100 100 100 100 20
Ethyl acetate 100 100 100 100 100
n-Butanol _ 100 100 100 100 100 35
Benzene 100 100 100 100 100 35
Toluene 100 100 100 100 100 100
* _ - - - - - -
ra-C 13 65 65 65 100 100 100
n-C14 46 46 46 100 100 100
11-C 15 25 25 25 100 100 100
11-C16
8 8 8 100 100 100
.11-C17
1 1 1 100 100 100
ri-C18
0 0 0 100 100 100
*Styrene, ethylbenzene, xylene, pyridine, chlorophenol, alkanes, alkenes from C
7 -C12 had 100%.
Table II. Recovery (percent) of Organic Compounds from Air Samples Using Carbopack B and Tenax-GC Traps.
- 13 -
d) Miscellaneous Adsorption Techniques
Activated alumina [77] and molecular sieve 5A [30] have
also been used to trap volatile organic compounds from the
atmosphere. However, both materials tend to irreversibly
adsorb some of the higher molecular weight labile components
and to show the same disadvangages as silica.
(iii) Solvent Trapping
Solvent scrubbing of organic components from air [74]
has met with only limited success. The reduction of solvent
volume in order to achieve the required final concentration
may be accomplished with minimal losses of high boiling
components but significant losses of volatile compounds do
occur.
The design by Goldberg et al [78], of a closed loop
solvent extraction system for trace organic compounds in
water, has enbabled the concentration of components by a
factor of 10,000. The system operates with any water-
immiscible solvent, however, the selectivity of the solvent
for particular compound classes and the high losses
associated with concentration, as mentioned above, tend to
limit the applicability of the method.
Grob [79] refined the solvent extraction procedure and
extracted 1 litre of tap water with 200 microlitres of n-
pentane and evaporated the solvent to 3 microlitres for one
GC injection. (Figure II). Over fifty components were
separated and identified by this method.
- 14 -
Figure II. GC Traces of Pentane Extracts of Water Samples [79].
Column: 2 m x 1/8" steel column, with 4 % Carbowax 20 M on Chromosorb G. AW-DMCS, 80-100 mesh
Column temperature: 65 °C Sampling capillary: 150 °C Carrier gas: Argon 28 ml/min Scavenger gas: 100 ml/min,
95 % argon. 5 % methane Detector: ECD Ni63, 1 nA Attenuation: x 64 Sample temperature: 90 `C Sample: 1 ml pale ale.
injection time 8 sec Components:
1 = diacetyl (approx. 0.08 mg/I)
2 = pentan-2.3-dione
fir
Head Space Analysis of Beer The head space technique has also proved to be a valuable tool for beer analysis. The two chromato-grams shown below demonstrate practical application in routine operation. The left-hand figure (A) gives the detection of the higher alcohols and esters, and the right-hand figure (3) shows the selective detection of vicinal diketones with art ECD.
Column: 2 m x 1/8" steel column, with 15 % Carbowax 1 500 on kieselguhr
Column temperature: 60 °C • Detector: FID Attenuation: x 2 Sample temperature: 40 'C
Use Of the Head Space Technique for Environmental Analysis Detection of hydrocarbons in waste water Column: 2 m x 1/8" column, packed
with 15 % polyethylene glycol on kieselguhr
Column temperature: 60 'C Detector: FID Attenuation: x 4 Sample: 10 ml water Sample temperature: 75 'C B = benzene 0.2 ppm T = toluene 0.5 ppm o-X = onhoxylene 0.1 ppm
- 15 -
B. Direct Headspace Collection.
Headspace collection and analysis of volatile organic
compounds is applicable if the concentration of the
components is sufficient for direct detection by the
analysing system. Hence, for GC analysis, one of the
previously mentioned concentration steps is often employed.
Headspace sample collection is a simple, effective method of •
analysing volatile components in a closed vessel. A number
of automatic and semi-automatic systems for syringe
headspace GC analysis are now available commercially [80]
following earlier work by Kolb, Novak and others [81-82].
Figure III illustrates applications of the technique to a
number of different sample types.
30 A 2'0 1 .0 0 mon 15
Figure III. Headspace Analysis of Volatile Components [80].
The headspace sample is drawn from a closed vessel by
means of a gas tight syringe needle through a silicon rubber
or PTFE seal [83,84]. Careful temperature and gas flow
control is required in order to obtain reprodilcable results.
- 16-
Problems with adsorption onto the septum may be encountered
with some volatiles and solvents [85-87]. This effect may
be minimised by use of the more expensive but inert PTFE
seals.
Injection of total headspace volatiles was undertaken by
Loper [88] utilising a heated gas tight syringe in his
examination of alfalfa flowers. Many other applications of
routine headspace analysis are being developed. The chief
advantage being speed in a quality control situation where
samples such as blood alcohol, plastic volatiles, obnoxious
odours, plant ripening volatiles [80,89] are to be
monitored.
- 17-
C. Separation and Analytical Techniques.
The introduction of capillary GC separation techniques
and mass spectrometer-computer data systems, has enabled the
separation and identification of complex mixtures of
volatile organic compounds that would previously have been
very difficult. Examples include the separation of
automobile exhaust and miscellaneous background volatiles
from ambient air [2,75], and human expired air volatiles
[73].
Development work is continuing on the coupling of liquid
chromatographic systems to the mass spectrometer to extend
the variety of sample types capable of being introduced to
this sensitive identification equipment [90].
i) Separation Techniques
Efficient separation of closely related chemical
compounds in complex mixtures is a necessary prerequisite to
positive identification. Unfortunately it is not always
possible to achieve this objective. In many instances
therefore, only a probability of component identification
can be assigned.
a) Gas Chromatography
Capillary GC columns, to date, have provided the most
effective system for the separation of complex mixtures of
volatile organic compounds [91,92]. The characteristics of
small sample requirement, high resolution, lower temperature
and speed make the use of capillary GC columns especially
- 18-
useful. Opposed to this, glass capillary columns are
relatively fragile, require special techniques for
preparation that are normally outside the scope of the
average laboratory, and require somewhat complicated
plumbing arrangements within the GC. Glass capillary
columns are usually drawn from borosilicate or soft glass
that contain levels of metal oxides that may catalyse
stationary phase decomposition at elevated temperatures,
resulting in column bleed.
The use of vitreous silica instead of glass as a column
material provides the efficiency and resolution
characteristics of glass columns while offering improved
inertness, thermal stability, flexibility and mechanical
strength [93,94]. The flexibility allows the positioning of
the end of the GC column through the GC-mass spectrometer
interface to a point adjacent to the ion source [95] thus
reducing the peak broadening effects associated with normal
interface systems. Silica capillary columns are being used
in diverse areas of medical [96], environmental [97] and
flavour analysis [98] to provide resolution of complex
mixtures of volatile components. The wide acceptance of
silica columns is shown by the number of papers presented on
this subject in the 1982 "Pittsburg" Conference held in the
U.S.A. [99]. (Five papers from a total of twelve in the
subject of Gas Chromatography).
The sharpness of peaks in capillary chromatograms often
allows measurement of quantities of materials which would
escape detection when eluted as broad bands of equal area
- 19-
from packed columns [100].
Temperature programming is usually employed due to the
wide range of boiling points represented in complex
mixtUres. Sub-ambient temperature programming has been used
by a number of authors [101] for separation of low boiling
compounds. The advantages of capacity of packed columns and
the efficiency of capillary columns has been utilised by
Blass et al [102] in a versatile combined configuration that
allows repetitive trapping and a number of other operations
within the one GC oven. Figure IV illustrates the
connections required to perform packed column operation,
capillary column operation, or combinations of the two. A
relatively large quantity of a mixture may be injected onto
the packed column and some components held by the trap TD
for further separation on the capillary column.
Figure IV. Two Column GC System - Packed and Capillary with Valve Switching [102].
PPC - Packed Column. CC - Capillary Column. D 1/2 - Detectors. I - Injectors.
Switching Valves, Needle Valves, and Filters.
- 20 -
Development of sampling techniques for trace volatile
organics from atmospheric sources [54,72,103] complements
the recent advances in capillary gas chromatography. Due to
the very fine detail discernible in complex mixtures,
capillary columns find a number of applications in
'fingerprinting' or source tracing in forensic science and
other fields. Examples include identification of oil spills '
[104], air pollution sources [105] and the origin of
Cannabis plant material [106].
Capillary columns may be considered under two headings -
SCOT columns are Support Coated Open Tubular columns with an
internal diameter of 0.5mm, where fine solid particles of
diatomaceous earth support, coated with a film of stationary
phase, are distributed evenly over the wall of the column.
They are suited to the analysis of volatile samples
[107,108] and are capable of accepting a greater sample load
than WCOT columns. Wall Coated Open Tubular columns have an
internal diameter of approximately 0.25mm and are used where
maximum resolution is required. A thin film of liquid phase
of 0.2 to 0.7 micron thickness is deposited on the inner
surface of the column. The inner wall is etched to provide
the correct surface properties and good mechanical support
for the liquid phase. Due to the thin film of liquid phase
the loading of this column type is restricted in comparison
to SCOT and packed columns. An inlet splitter is frequently
used to deposit the optimum quantity of material onto the
column - the remainder of the sample or solvent being
vented.
- 21 -
b) Mass Spectrometry (MIKES)
The mass spectrometer may be used as an efficient
separation/ identification tool when coupled to data
reduction and library search computer facilities. The direct
introduction of a complex mixture of volatile components
into a MS, the use of computer controlled scanning and
selected ion monitoring, has enabled the separation and
identification of components [109], and the study of
reactions and reaction mixtures [110,111]. The method is
based on the mass-analysed ion kinetic energy spectrometer
(MIKES) first described by Beynon et al in 1973 [112].
Sample preparation is minimal - in some cases none at all -
and the technique is useful for structural elucidation.
However, quantitation has been difficult to achieve [113]
and further developments are required to make the technique
amenable to routine work.
c) High Performance Liquid Chromatography
High performance liquid chromatography (HPLC) has not
been widely used An the past as a separating method for
volatile organic mixtures. However, recent advances in HPLC
technology have made the technique comparable to GC in
speed, convenience and efficiency [114,115]. The chief
advantage of HPLC is the fact that milder solventrand thermal conditions
may be employed for the separation of labile components that
may decompose under harsher GC temperatures. Precursers of
many volatile components are labile and HPLC .could prove to
be of value in determining breakdown pathways -. One of the
- 22 -
disadvantages of HPLC has been that the separation
efficiency of HPLC columns (approximately) 7,000 theoretical
plates) has been a lot lower than the 120,000 theoretical
plates of silica capillary GC columns. Recycling of the
column effluent and the use of microbore columns can improve
the resolution [116]. However, peak capacity is reduced and
complex mixtures with a wide range of boiling points cannot .
be effectively separated by this procedure.
HPLC has been widely used for the separation of polynuclear
aromatic compounds in airborne particulate material [117],
and to complement and extend the determination of this class
of compounds in conjunction with GC techniques [118].
d) Miscellaneous Separation Techniques
Gel permeation chromatography [119] has been used for
separation and molecular weight determination of labile
substance of similar molecular size [120]. Hendrickson
[121] referred to the method as "a new basic tool that could
be called a liquid phase size spectrometer". However, this
chromatography technique is applicable to compounds of high
molecular weight and low volatility.
Liquid-liquid extraction systems are now available
commercially as counter- current chromatography apparatus.
Claims are made [127] that the method combines the benefits
of countercurrent distribution apparatus and liquid
chromatography, with minimium sample loss, no contamination
from solid supports and no tailing of solute peaks due to
- 23 -
adsorption effects. Other liquid chromatography techniques
such as droplet counter- current chromatography [122] have
separation efficiencies close to that of GC, but also have
limited applicability in trace volatile separations except
where, as above, labile components are encountered.
Liquid-liquid fractionation techniques are frequently
used as preliminary separation steps where complex mixtures
of organic compounds are separated into various classes
[123-125]. The combination of chemical information obtained
by fractionation, GC and/or HPLC retention data coupled with
spectroscopic information is usually sufficient to identify
components of complex mixtures with reasonable certainty
[126]. The disadvantages of fractionation methods of sample
separation are twofold, involving the efficiency of
separation under slightly differing conditions, and problems
concerning the formation of artifacts or the introduction of
impurities. Many authours fail to provide data on these
aspects of the technique [126].
Programmed multiple development chromatography (PMD) is
a method of processing thin layer chromatography
plates[128-132] to improve resolution and sensitivity. A
system of sequential solvent advance and evaporation ensures
reconcentration of spot material along the axis of 'solvent
motion, producing a thin band rather than a diffuse spot.
Advantages claimed are:- shorter development times, improved
resolution of up to 50 times compared with conventional TLC,
sensitivity improvement of 5 to 10,and a greater tolerance
-24 -
to overloading. Most of the above techniques have only
limited applicability to volatile trace organic separation
systems.
- 25-
D. Detection and Analytical Techniques.
Trace volatile components eluted from a GC are usually
identified according to the retention time compared to a
standard under identical conditions. Incorrect
identification may result if several compounds elute at the
same time, or if a massive amount of solvent alters
conditions in the column.
• The flame ionisation detector combines sensitivity and
versatility for trace compound detection. However a range
of on-line spectroscopic detectors is available [133]; and
the selectivity of the electron capture [134] and flame
photometric [135] detector is widely utilised. Development
of a helium microwave emission detector [136-138] has
enabled the determination of trihalomethanes in 10 ml of
drinking water to levels of 1 part per billion [139].
The most powerful combination for separation, structural
determination and quantitation is thecapillary GC/MS -
computer system [21], [91 - 92], [140-144]. This combination
is capable of the separation and identification of complex
mixtures of volatile organic materials in a variety of
matrices [145-146]. The data processing capability allows
the storage, retrieval and tentative identification of
several hundred component peaks of a complex mixture
[147-148], [149-150].
Data processing systems coupled. to GC/MS can.be used to
resolve overlapping GC peaks and to counteract unwanted
. SO
Scan Number
rnis
Individual " t Mass -251 Chromatograms Reconstituted
Mass Spectra 4.5
1St
ORIGINAL GAS CHROMATOGRAM
LS
Mass Reconstituted Gas Chromatogram
Scan Number
• 7.
- 26 -
contributions from column and septum bleed that would
otherwise distort the relative intensities of ions in the
mass spectrum [151-153]. The resolving effect relies upon
the distinction between the MS parent ion peaks, which may
be detected even though the original GC peaks were over-
lapping (see Figure V). Usually 5-10 mass spectra can be
collected per GC peak and this provides enough information
for processing and reconstruction of a resolved mass
chromatogram.
Figure V. Complex Peak Resolution by MS-Computer Techniques.
- 27 -
Sweeley and co-workers have developed methods for
separating complex mixtures using computer programs to
control repetitive scanning and selected ion monitoring
[154]. They have developed a system that incorporates the
use of retention indices with off-line reverse library
searching of selected mass chromatograms from repetitive
scanning of the GC/MS of complex mixtures. Observed
precision of retention index was 0.2 percent and lower limit
of detection lOng. The GC/MS precision was 8 percent within
duplicate detection of the same sample and the linear range
for quantitative ananlyses was 1,000 fold [155].
The most significant, advance in techniques in this field
have been the combined utilisation of the developments of
splitless sample injection, the preparation [156], and
evaluation [157] of the operation and performance of WCOT
columns, open split injection [158] and direct connection of
the GC capillary to the ion source of the mass spectrometer.
Other detection and analysis techniques for monitoring
volatile components include; Fourier transform spectroscopy
[159-161] using folded path optics for the measurement of 10
ppb levels of hydrocarbon and other species; infrared
spectrometry coupled with microprocessor control [162],
chemiluminescence [163] as well as a variety of laser based
systems [164-165].
Vapour phase infrared spectrophotometric.detection of GC
eluant peaks [166] using on line computer techniques has
- 28 -
recently shown to be effective in some applications where
mass spectral techniques are inadequate [167].
Ancillary techniques, or modified computer search
methods, need to be utilised if positive identification of
some components is required. Comparison of published mass
spectra of terpenes [168], for example, indicate that
structurally different terpenes such as tricyclene, alpha-
pinene, and 3-carene show differences only in ion .
intensities of the principle ion peaks with identical mass.
These differences are often within the normal operational
variables if there are other contributing factors such as GC
column bleed or incomplete peak resolution and hence,
unequivocal identification by mass spectral means alone is
not possible [169].
So rapid are the changes in GC/MS - data system
applications that the quantity of literature published in
the field of trace organic analysis using this combination
of techniques is extremely difficult to scan. The various
reviews in Analytical Chemistry provide a useful method of
gaining some overview of the topic. A summary of detection
systems for trace organic volatiles may be found in the
Application Reviews of Analytical Chemistry [170] and also
under the specific headings of Mass Spectrometry [171] and
Gas Chromatography [172] in the Fundamental Reviews.
- 29 -
E. Sources of Error in Trace Volatile Analysis.
Many organic compounds present in air and water are
labile and the method of sampling will influence the
qualitative and quantitative result of any analytical
programme. The use of complementary techniques for sampling
and analysis and the choice of conditions that tend to keep •
decomposition and rearrangements to a minimum should be
utilised wherever possible. Contamination of a sample at
any stage of the collection analysis chain may lead to false
assumptions and costly errors. A well documented example
was the contamination of lunar rock samples [173-175] and
the difficulty in establishing if the substance measured was
a contaminant or otherwise.
An accurate measurement has been defined [176] as a
precise numerical value that is free of, or corrected for,
all systematic errors. In order to attain such a result,
all aspects of sample collection, storage, extraction,
concentration, isolation, identification, and quantitation
must be examined. Lewis [177] has discussed some of these
problems with special emphasis on trace organic analysis.
The correct choice of sampling method to ensure a
respresentative sample depends on factors such as
representative volumes, times and avoidance of contamination
by the sample collection and analysis method. Each
succeeding step should be undertaken in the shortest
practical time, however if storage is necessary a
- 30 -
temperature of 0 deg.0 or less should be chosen to minimise
effects of photo- decomposition, microbiological action, and
chemical interaction between components and container [178].
During the extraction of volatile components from air
and water, contamination and losses may occur from a number
of sources; solvents and solid extraction systems contain
impurities, and extraction efficiencies are often
considerably less than and extraction efficiencies are often
100 percent, especially where a wide range of compound types
are involved. If a solvent extraction procedure is employed
the components in the solvent may require concentration
prior to analysis. Loss of volatile components and reaction
of labile compounds often occurs as a result of this step.
The use of Kuderna-Danish concentrator [179] can help to
minimise the loss of volatiles provided care is taken in
heating and the choice of solvent. Concentration to
approximately 50 microlitres is possible with a micro-
Kuderna-Danish concentrator. XAD and Tenax resins are also
used to concentrate components as outlined previously,
however volatile losses may also be significant using this
technique and should be monitored where possible.
Problems with isolation of individual components
involving rearrangements, irreversible adsorption,
decomposition and incomplete separation are common to
chromatographic and MS methods. Optimisation of
instrumental parameters and correct choice of technique for
the sample type will help to minimise many of the effects
mentioned.
-31 -
Identification of a component by comparison with
properties of a previously measured known compound may be
extremely difficult where complex mixtures of trace organic
materials are to be analysed e.g. drug, food and plant and
pesticide breakdown products. Pure standards for these
compounds are often not available to allow addition
techniques to be employed for positive identification.
Combined GC/MS systems employing internal standards
incorporating carbon 14 have been extensively utilised
[180] as an internal quality control system. Addition of an
isotope labelled labelled compound is an effective method
for the determination of losses of components during
subsequent extraction, concentration and isolation steps.
Isotope labelling cannot, however, be undertaken for each
component in a complex mixture and differences in chemical
nature between compounds can cause variations in recoveries.
One compound of each class likely to be present should be
selected to check on recoveries through the system.
A variety of methods have been employed to assess
accuracy in trace organic analysis [178]. These include
collaborative laboratory studies, analysis of spiked samples
and inter-laboratory comparisons [181]. Many of these
studies have shown the need for more extensive in-laboratory
quality control checks, and the necessity for the
development of a wide range of appropriate Standard
Reference Materials [182].
-32 -
CHAPTER III
,DEVELOPMENT OF A SAMPLING SYSTEM FOR VOLATILE
ORGANIC MIXTURES.
Introduction.
A simple method of sampling volatile compounds from a
variety of sources is required in many applied areas of
chemistry. The detection and analysis for example, of
volatile solvents in paint spraying industries, odour
tracing in environmental problem areas, and plant volatiles
for the perfume and flavour indistries are some typical
examples where the use of a rapid routine method of
collection and analysis of volatile compounds would be of
advantage.
Ideally a sampling system should be capable of trapping
quantitatively and reproducably a wide range of chemical
compounds in sufficient quantity to give an accurate
analytical assessment. The trapping method should not
degrade or alter the collected components on collection,
storage or elution. The above properties of a trapping
system are often difficult to effectively check,
particularly in the case of complex mixture trapping. Upon
• adsorption, there is a possibility of chemical reaction
between the components trapped, due to the higher
concentration in the medium, with other species and also
with the trapping medium.
- 33 -
investigation of the available information in the literature
was made in order to select the adsorbants with the most
favourable characteristics. An outline of this literature
search is provided in the previous chapter. A number of
different sample collection and elution methods were
selected, tried and some rejected, as described in the
following pages.
-34 -
A. Selection of a Sample Adsorption Medium.
(i) Carbon,
The efficiency of carbon as a trapping material in the
form of 25mg charcoal disks, as demonstrated by Grob [21],
prompted the investigation of this material as a trapping
medium for the collection of organics from ambient and
contaminated air. Difficulties encountered involved the
manufacture of a consistant porous charcoal filter that was
mechanically rigid enough to withstand the force of the air
passing through the structure. The original commercial disks
as described by Grob were not readily available. Various
modifications of a dye press were tried and varying amounts
of heat were applied to the carbon in order to obtain a
consistant useable product - without a great deal of
success.
Crushed granular carbon (activated charcoal) from B.D.H.
Ltd. U.K., "Special for Gas Adsorption", of two screen sizes
was cleaned by Soxhlet extraction with methanol and
dichloromethane as solvents. Each size fraction was packed
into 9mm diameter by 95mm long glass tubes with a 310 cone
at one end and held in position by glass wool plugs at the
ends. Material similar to this is extensively utilised for
removing organics from air in gas masks[190].
Recovery checks on a range of compounds yielded the
information in Table III. The test compounds were
introduced into a flowing nitrogen carrier gas stream by
- 35 -
controlled addition using a Waters HPLC pump feeding into a
mixing vessel. The liquid sample flow rate in conjunction
with the gas flow rate was adjusted to give a concentration
of 100 p m (Figure VI).
1 hi
Figure VI. Flow Diagram of Recovery Test Apparatus.
1. HPLC pump. 2. Thermostated mixing vessel. 3. Carrier gas inlet valve and flowmeter. 4. Bleed valve and flowmeter. 5. Sample trap. 6. F.I. detector.
Size Fraction -10+20 Mesh -200+250 Mesh
Pentane 95 98 Hexane 96 96 Acetone 85 92 Methanol 92 93 Ethanol 83 87 Benzene 82 86 Ethyl acetate 78 68 Carbon tetrachloride 83 86 Diethylamine 64 58
Table III. Percentage Recovery Test Activated Charcoal Adsorbent. Test Compounds at a Concentration of 100ppm.
The flame ionisation detector of the GC was used to
determine the breakthrough of the test compound and the
sample tube was then removed for solvent extraction and
recovery. A second recovery check was made by adding one
microliter of the steam distillate of Pinus radiata to the
top of the column and washing in with 500 microliters of
- 36 -
carbon disulphide. Extraction from the activated charcoal
was accomplished by refluxing 5mL of carbon disulphide
using a cold finger apparatus as shown in Figure VI. The
small volume refluxing through the trap reduced the
concentration of the impurities upon solvent reduction in
the micro Snyder distillation (Figure VII). An internal
standard of n-decane was added to the carbon disulphide at
the completion of the extraction to enable allowances for
some of the losses likely to take place during the solvent
reduction step in the concentration apparatus.
Recovery of the lower molecular weight components of the
test compounds was quite acceptable but losses of higher
molecular weight components, especially oxygenated terpenes
of the radiata pine oil, was unacceptable. For this reason
the use of activated charcoal was not continued.
2.
Figure VIIa. Micro Reflux Apparatus.
1. Cold Finger. 2. Sample Tube. 3. Solvent Flask (10mL).
. 2.
Figure VIIb. Snyder Concentration Apparatus.
-37 -
1. Snyder Distillation Column. 2. Heat Shield Covered With Al
Foil. 3. Graduated and Calibrated Taper. 4. Hot Plate.
- 38 -
ii) Tenax GC
Tenax-GC has been widely utilised for the concentration
of trace organic compounds in air as described in the
previous chapter. Tenax (poly-p-2,4-diphenylphenylenoxide)
has the structure shown in Figure VIII and the manufacturers
claim it is stable up to temperatures of 350 deg.C.
Figure VIII. Chemical Structure of Tenax GC.
The thermal stability and hydrophobic nature of the
material coupled with the ability to trap a wide range of
organic compounds would appear to make Tenax a favourable
choice as an adsorbant.
Tenax was prepared by conditioning overnight at 325
deg.0 in a wide bore glass tube in a stream of high purity
nitrogen. The packing was stored in capped glass containers
prior to packing in sample tubes and then reconditioned at
275 deg.0 before use.
Recovery Checks. Pellizzari et al [63], have recorded
the breakthrough volumes of a number of volatile organic
compounds. Checks were made on many of the figures
presented using a 4mm internal diameter by 170mm long glass
tube packed with Tenax (Table IV). The results shown were
- 39 -
calculated back to 2.15g of Tenax for comparison [187].
There was substantial agreement for all compounds except
acrolein. Apparatus used for the test was similar to that
of Figure V.
Breakthrough Volume (L)* Compound 2.159 Tenax 2.87g Tenax Lab.
Comparison
Acrolein 9 13 3 Propylene oxide 15 20 15 Diethyl sulfate 19 25 18 Trichloroethylene 50 - 52 Nitromethane 86 114 87 Glycidaldehyde 147 195 - Chlorobenzene 300 - 310 B-propiolactone 330 440 Bis-(chloromethyl)ether 400 530 Butadiene diepoxide 646 860 Cyclohexene oxide 1,040 1,380 1,100 N-nitrosodiethylamine 1,220 1,620 1,200 Aniline 2,100 2,800 2,250 Ethyl methanesulfonate 2,420 3,220 - Styrene oxide 7,550 10,000 7,600 Acetophenone 2,880 3,380 2,850
*Volume required to elute one-half of adsorbed vapour at 25 deg.C.
Table IV. Breakthrough Volumes for Several Highly Volatile Compounds on Tenax GC (40/60 Mesh) Cartridges
Janak [188] and other authors, have confirmed the
negligible influence of water vapour on the trapping and
elution efficiency of Tenax. Tests conducted in this
laboratory at 50% and 70% humidity levels, using steam
distillate of Pinus radiata bark oil, showed no alteration
of trapping and recovery efficiency.
- 40 -
B. Development of Sample Collection and Desorption Equipment.
i) Sample Collection
Optimum sample collection efficiency is dependent on
factors such as gas flow rate, rate of diffusion of sorbate
into the pores, particle size and shape, bed geometry,
porosity and temperature [187]. The geometry of the sample
collection tube was limited by mechanical aspects of the
desorption apparatus as well as theoretical considerations.
The equipment used to collect volatile organics from air
samples consisted of:- 1. a Pyrex glass or metal tube packed
centrally with 40-60 mesh Tenax held in position with
silanised glass wool. The weight of Tenax per sample tube
was 0.40g. 2. A calibrated flowmeter measured the rate of
gas passing through the sample tube. 3. An electrically
driven diaphragm pump was used to draw the gas through the
system (Figure IX).
• . •
3 ..
Figure IX. Flow Diagram of Apparatus for Sampling of Volatile Organic Compounds.
1. Glass Tenax trap. 2. Calibrated Flowmeter. 3. Diaphragm pump.
Flow rate for sample collection was 30-50 mL per minute
and the temperature of the sample tube was maintained at or
below 20 deg.0 (by a water cooled jacket if required).
- 41 -
ii) Sample Desorption
The requirements for thermal desorption and injection of
the sample into a GC include quantitative removal of the
sample from the collection medium, and rapid injection of
the vapour into the inlet of the GC without bleed during
secondary trapping.
A trapping system described by Houghton [189] and
illustrated in Figure X, was constructed with some
modifications. A luer adapter was silver soldered onto a
6mm Swagelock fitting to allow the connection of a syringe
needle to the metal sample tube using a compression Graphlok
seal. The equipment consists of a heating coil mounted on
two metal formers with a gap between to allow the insertion
of hot or cold metal probes [190]._
A
El Glass Wool Coated Packing
ari Asbestos Jacket Yi.j: Asbestos Tape
• Nichrome Wire
-7-Figure X. Initial Thermal 'Desorption Apparatus [190]. (A) .Stainless-steel collection tube; (B) cross section
of the collection-tube heater with tube in position.
The sample tube was partially inserted into the
apparatus and a syringe needle attached and inserted into
- 42 -
the septum of the GC. The carrier gas line was attached by
a second Swagelok fitting to the other end of the sample
trap. Heat was applied to the tube by the passage of an
electric current through the heater windings and the
application of a liquid nitrogen cooled trap prevented the
passage of the components into the GC. When the system
reached a steady temperature of 200 deg.0 the cold probe was •
removed and a hot probe placed in the same position. The
carrier gas from the GC at the same time being diverted
through the sample tube to flush the components into the GC.
The system was found to function efficiently for a
single component in air samples and was very good for
isolating single peaks from a GC run. (This was
accomplished using a heated column switching valve to divert
the carrier gas flow from the FID to the trap at the
expected elution time of the peak. A component collected in
this manner could be reinjected into the GC onto a different
column to check for purity:) Problems were encountered
however, with complex mixtures of components with similar
boiling points giving rise to overlapping peaks and poor
recoveries (Figure XI). The trace is of a sample taken from
an organic teaching store exhaust air stream.
FID
Resp
onse
•
20 0 4 8
200 12 16
250 Temp. °C 20 24 Time (mins)
-43-
Figure XI. GC Trace of Trapped and Injected Volatile Organic Compounds in Air (2m OV101 GC Column, 120-260 deg. C at 5 deg./min. Air Sampled 1.96L 20 deg. C )
The problem with the technique appeared to be the
inefficient transfer of heat to the sample tube resulting in
lack of resolution on the analytical column. A variety of
columns, including capillary columns, were used but with no
major improvement in resolving power.
Redesign of the system to give better heat transfer and
improved cold trapping appeared to be necessary. The heating
block was constructed to enable continuous desorption of the
organic compounds as heat was applied, and flushing of the
components by the carrier gas stream to a cold trap
directly immersed in liquid nitrogen.
- 44 -
"2-
Figure XII. Thermal Desorption and Injection Apparatus.
1. 2mm Swagelock Fitting - carrier gas inlet. 2. Tenax Sample Tube. 3. Resistance Wire Round S. Steel Heating Block. 4. 6mm Swagelock Coupling and Electrical Connector. 5. 3m GLT. 6. Electrical Connector and Coupling to GC inlet. 7. GC Column.
A diagram of the equipment is shown in Figure XII.
The apparatus consists of a 25mm diameter stainless steel
cylinder (2), drilled through the centre to accept a 170mm
by 6mm sample collection tube, and off-center to accept a
thermocouple probe. The metal cylinder was covered with a
heating element consisting of 7.2m of 1.779 ohm/m in a
single layer of No. 20 gauge B. and S. resistance wire wound
over mica. Carrier gas tubing was connected to the 2mm
coupling at one end of the heater block (1), and the Tenax
sample tube was inserted intO the other end of the block
through a drilled out 6mm Swagelock fitting silver soldered
- 45 -
to the stainless steel. Gas sealing by a Graphlok ferrule
(4), also prevented the tube from being ejected as did the
coupling of the 3mm diamter glass lined metal U tube (5).
At each end of the U tube brass lugs were attached to
provide electrical connections for coupling to a welding
transformer. A number of different configurations of glass
lined metal U tube were manufactured, the use depending upon
the configuration of the inlet system of the GC or GC/MS
unit. A horizontal version with a luer fitting and a 20
guage needle was frequently used. The system illustrated
shows the 3m glass lined tubing (GLT) coupled directly to a
piece of 6mm GLT inserted into the inlet heater of the
GC/MS.
Cooling of the U tube involved placement of a small
insulated vessel filled with liquid nitrogen under the U
section of the tube. The apparatus was then coupled to the
carrier gas flow and the system purged of air for a few
minutes at a low flow rate. Optimum carrier gas flow
adjustments could be undertaken when the system was
connected to the GC inlet and then heating of the block
could commence. A power. supply of 50V from a variable
voltage transformer enabled the heating block to reach a
temperature of 200 deg.0 within 6 minutes. A chromel-alumel
thermocouple inserted into the stainless steel block was
used to monitor the desorption temperature. Thermal elution
times of 6 to 10 minutes proved to be adequate for most of
the volatile air samples trapped using Tenax: The carrier
gas transported the desorbed organics to the U tube section
-46 -
of GLT where secondary trapping (condensation) concentrated
the material.
Rapid injection of the organic mixture onto the GC
column involved resistance heating of the 3mm GLT by
connecting the secondary output from a welding transformer
across the two lugs, at points 5 and 6, immediately after
the removal of the liquid nitrogen bath. A current setting
of 40A applied for 30 seconds rapidly heated the GLT to a
maximum temperature of 300 deg.C, at a rate that ensured
breakage of the tubing did not occur.
Following a number of field trials, where mechanical
breakage of glass sample trap tubes had occured, the
decision was made to replace the glass with glass lined
stainless steel tubing of the same dimensions. The added
mechanical strength of the GLT also was an advantage in the
desorption apparatus where coupling of the 3mm U tube to the
desorption system had often placed an unacceptable degree of
strain on the glass tube. Heat transfer to the packing from
the heating block was also improved.
The redesign of the thermal desorption equipment, as
outlined above, improved the quality of the traces obtained
from the GC and GC/MS runs and enabled use of the method for
routine sampling of volatile mixtures in a number of areas
that would not have been possible using previously available
techniques.
-47 -
C. Blank Determinations and Sample Trap Storage. •
Introduction.
An important aspect of the sampling of trace volatile
organic compounds is the requirement to reduce the risk of
contamination of the collected sample. Contamination may
occur in a number of ways; from degradation of the
collecting material, from breakdown of the collected
components so that there is no resemblance to the original
sample; or, the ingress of chemicals, such as solvent
- vapours, from the handling or laboratory.
A number of instances occurred, in the course of the
investigations that are documented in the following pages,
where solvents such as chloroform and 'Freon' were detected
in collected air samples that should have been free of such
components. The steps that were followed to reduce the
contamination that tended to result from working in a
general purpose organic laboratory are described.
Experimental.
Tests were conducted on the desorption efficiency at 250
deg.0 and 300 deg.0 on portions of Tenax that had been
previously used fbr trapping terpene volatiles. One tube
was initially conditioned at 250 deg.0 for 60 minutes in a
stream of high purity nitrogen, and the other was
conditioned at 300 deg.0 under similar conditions. Each
sample tube was then placed in the stainless steel
desorption block at 250 deg.0 and 300 deg.0 respectively for
- 48 -
ten minutes and the eluted 'blank' run through the GC/MS
system. An OV101 WCOT 50m silica.column was used to
separate the components prior to entry into the MS system.
The GC/MS conditions are set out below:
Figure numbers XIII, XIV.
Carrier gas - hydrogen at 1.5 mL/min Temperature range 50-220 deg.0
Vacuum 10-6
Torr. 4 deg./min to scan 350 then 8 deg/min
The mass spectrometer system was adjusted to a
relatively high sensitivity range and calibrated to scan
from 0-350 mass units. The total ion current traces are
shown in Figures XIII, XIV. The components are listed in
Tables V and VI, the corresponding total ion current traces
are shown in Figures XIII and XIV.
253247
311
4
3PS
288 ege GEO 689 740
Csi7 19311 12321 16312C 29:21 22343 tea a:ItS
GS2
SG G 9
•-•
- 49 -
Figure XIII. Total Ion Current Trace Tenax Sample Tube Conditioned at 250 deg. C.
---r- r- • a I 2aa 229 489 Gee CO9 700
0:0 212S 01i7 12:20 12:22 IC: :18 22:44
Figure XIV. Total Ion Current Trace Tenax Sample Tube Conditioned at 300 deg. C.
- 50-
Scan No. Component
43 carbon dioxide
44 carbon dioxide plus unknown HC M. Wt 96
86 toluene
102 chloroethylene
176 monoterpene
204 monoterpene
206 monoterpene.
215 trimethyl benzene isomer
229 monoterpene
242 monoterpene M. Wt 134
249 monoterpene M. Wt 136
253 monoterpene
272 monoterpene
301 unknown
314 hydrocarbon
327 undecane - C11 hydrocarbon
364 menthofuran M. Wt 150
391 myrtenal
406 unknown - possibly a terpene
415 dodecane M. Wt 170
Table V. Compounds Eluted from Tenax Sample Tube Conditioned at 250 deg.C.
Scan No. Component
44 carbon dioxide
249-270 unresolved mixture of trace quantities of unknown mixture
451 unsaturated C10 aldehyde
516 decenal
539-585 unknown, mixture
598 trimethyl naphthalene
619 unknown mixture containing one branched HC
647 unknown ketone
649 heptadecene M. Wt 238
652 heptadecane M. Wt 240
655 branched HC - weak parent ion
679 octadecene M. Wt 252
682 octadecane M. Wt 254
712 nonadecane? or ecosane?
732 palmitic acid (carboxylid acid peaks 60 & 73)
Table VI. Compounds Eluted from Tenax Sample Tube Conditioned at 300 deg.C.
- 51 -
Discussion.
The results indicate that quantitative desorption does
not occur when the Tenax sample tube is heated to 250 deg.0
for trapped terpene components. The traces obtained
indicate that either a higher conditioning temperature, or,
a longer conditioning time is required to reduce the blank
contamination carry over level. Higher desorption
temperatures should improve the initial recovery percentage,
simultaneously reducing the conditioning required provided
that unacceptable levels of thermal breakdown products are
not generated. Desorption temperatures of 270 deg.0 and 290
deg.0 were used by Pellizzari [56] and Bertsch [19] for
recovery of components adsorbed onto Tenax.
A paper by a research group of the U.S. Air Force [192]
lists benzene as a major thermal breakdown product of Tenax
and as a result use a conditioning and desorption
temperature of 240 deg.C. The trace at 300 deg.0 (Figure
XIV) did not show any measurable quantity of benzene, this
would appear to contradict the work of the above authors who
claimed that the quantity of benzene trapped was directly
related to the conditioning temperature in excess of 250
deg.C. Tenax used in allthe traps packed had previously
been conditioned in this laboratory at 325 deg.0 under a
stream of high purity nitrogen for twelve hours. Treatment
at this temperature removed any loosely bound or unreacted
solvents and decreased the tendency to form voids in the
sample tubes. Glass Tenax analytical GC columns showed a
- 52-
tendency to form large visible voids unless the packing was
preconditioned in the above manner. Presumably the above
authors did not precondition at a temperature higher than
240 deg.0 and this may account for the continual loss of
benzene. At a desorption temperature of 240 deg.0
quantitation of components would also be somewhat difficult,
unless, a range of internal standards was added to the
original sample to enable collection efficiencies to be
calculated.
Conclusions.
Air sampling of volatile organic compounds by the use of
a Tenax sample tube should be undertaken with due regard to
the possible effects of conditioning temperature and time.
Care should be exercised in the initial preconditioning of
the packing material. A blank run should be conducted on
the tube prior to dispatch to the sampling area and a
similar blank tube should accompany the sample tubes.
Sample tubes should be stored individually in glass
stoppered carrying containers with a small quantity of
dried silica gel. Where possible Tenax sample tubes should
be allocated to one particular sample type; i.e. one set of
tubes for ambient air monitoring, one set for volatile
terpenes etc.
The use of glass lined metal tubing for Tenax sample
tubes provides the mechanical strength of steel with the
inert properties of glass and has proved most satisfactory
% Inte
nsit
. tim'aMnV3.
Explanatory Diagram of MS Total Ion Current Trace.
- 53 -
for field sampling. The procedure adopted to reduce cross
contamination of sample collection tubes involved the
following: the GLT was baked in a furnace at 600 deg.C,
packed with the preconditioned Tenax, and reconditioned at
300 deg.0 immediately before despatch to the sampling point
in glass stoppered tubes. The sample trap could be stored
for up to two weeks in a cool room without loss of sample,
however processing was generally undertaken as soon as
possible following collection of the sample.
Note. Interpretation of MS total ion current trace. The information from the ion current scans is stored in the data system and the output intensity is calculated relative to 100 percent of the highest peak - unless overloading occurs. The output trace is percentage intensity (vertical axis) vs scan number with time in decimal minutes printed below (horizontal axis). Prominant peaks are labelled with the respective scan numbers (X1,X2,etc). Details of the MS equipment used are provided in Table VII, and in the appendix.
- 54 -
CHAPTER IV
AN EXPERIMENTAL COMPARISON OF VOLATILE ORGANIC
SAMPLING TECHNIQUES.
Introduction.
Exposure to mixtures of volatile organic components has
become an accepted part of normal living experiences and
little attention is paid to various odours unless they are
particularly obnoxious or dangerous. Irritant effects at
low concentration in the air of working environments can be
tolerated with some compounds but not with others.
Assistance with the qualitative determination of an
irritant that was present in-the atmosphere surrounding a
furnace was requested from industry. The persistant, mildly
lachrimatory, eye irritant nature of the substance made
working conditions in the vicinity of the furnace
particularly unpleasant. Conventional methods of detecting
the compound type, i.e. by use of commercially available gas
detection equipment (Draager Tubes etc.) had failed.
This request provided an ideal case study to compare
four different sampling and concentration techniques:-
a) Direct gas sample collection in a Teflon bag
b) Solvent adsorption
, c) Cryogenic trapping
d) Tenax sample tube adsorption.
- 55 -
A. Experimental
The furnace consisted of a rotating steel drum heated to
180 deg.0 by a liquified petroleum gas flame. Modifications
had been made to the burner upon the recent installation of
the unit. Heat loss from the gas flame was minimised by
three different types of thermal insulation that were placed
on the inside of the support structure adjacent to the flame •
area. Hot air from the flame jet rose around the outside of
the rotating furnace and was conveyed by a duct to the
outside of the building. Round the front of the rotating
drum of the furnace was a rubber flap to minimise heat loss,
however, a certain amount of hot gas escaped at this point
and thus carried quantities of the irritating component into
the atmosphere of the room. (Figure XVa) Considerable
discomfort caused by irritation of the face skin, and
lachimatory action to the eyes, occured whilst sampling the
hot gas stream. The effect was somewhat similar to that of
low concentrations of acetyl chloride.
Figure XVa. Front Elevation of Furnace.
1.Gas Flame 2.Glass Fiber Insulation 3.Rubber Seal 4.Rotating Cylinder
- 56-
i) Sampling
All glassware used was cleaned by washing with
detergent, rinsed with distilled water and then heated to
600 deg.0 in a furnace. The solvent used was redistilled
AR. dichloromethane, and where direct adsorption was not
possible Teflon tubing was used to convey the gases.
a) Direct Gas Sampling
Gases escaping through the top of the rubber seal round
the drum of the furnace were sampled directly into a 300 x
300 mm Teflon gas ample bag and the bag sealed with a Teflon
faced septum. This was accomplished by placing the empty
Teflon bag into a 20L plastic barrel with the inlet of the
bag projecting through the lid of the barrel. Air was
withdrawn from the barrel. The resulting decrease in
pressure expanded the bag inside the barrel and allowed the
collection of several litres of sample.
b) Solvent Adsorption
A Venturi water pump was used to draw the sample gases
through two Dreschel bottles in series containing a total of
200mL of the dichloromethane solvent. The Dreschel bottles
were immersed in a water-ice mixture to prevent rapid loss
of the solvent due to evaporation, and gases were ducted to
the system via Teflon tubing. The flow rate was 30L per
hour and sampling continued for two hours.
- 57 -
c) Cryogenic Trapping
A sample of the gas mixture was drawn through a glass U
tube immersed in liquid nitrogen within a Dewar flask to
condense volatile material. The U tube was washed out with
dichloromethane at frequent intervals to ensure that as much
as possible of the condensed organic material was retained.
The volume of gas mixture sampled was 20L. Problems
encountered included frequent ice buildup in the U tube
resulting in blockage of the flow line, and the difficulty
of disconnecting and reconnecting tubing that was rigid at
the low temperature.
d) Tenax Sample Tube
Gases emanating from the furnace were at a temperature
in excess of one hundred degrees, therefore, in order to
retain volatile components on the Tenax sample tube, a
method of cooling was required. This was accomplished by
inserting the sample collecting tube into a water jacketed
length of 8mm diamter copper tube surrounded by a cooling
water jacket (Figure XVb). The temperature of the glass
Tenax tube was therefore maintained at less than twenty
degrees enabling the adsorption of low boiling point
components. The sample tube was held in position by a 6mm
Swagelok fitting silver soldered onto the end of the copper
tube.
-5 8-
dormammumar umwm. ammairmamnrAmmaci
•
• • tf
• / /
5. _
Figure XVb. Water Cooled Sample Collection Probe (Cross-section).
1. Tenax sample tube. 2. Hot gaseous sample in. 3. Cooled gas out. 4. Cooling water inlet. 5. Cooling water •outlet. __6. Cooling water jacket. 7. 6mm Swagelok coupling. 8. Aluminium foil wrapped over
fiber glass insulation.
The inlet of the Tenax sample tube, in the water cooled
jacket, was suspended above the furnace adjacent to the
rubber seal. A flow rate of 50mL per minute was maintained
through the sample tube for two hours.
ii) Analytical results
Analytical work on the collected samples was undertaken
using packed columns on the GC and capillary columns on the
GC/MS runs. Sample pretreatment of the solvent collected
samples consisted of careful evaporation under a controlled
stream of high purity nitrogen gas at 30 deg.C.
a) Direct Gas Sampling
A 2.0mL portion of the gas sample was injected onto a
packed GC column (3 percent Dexil 300 on 100-120 mesh
Chromosorb W HP). A gas tight syringe was used to transfer
the sample to the 2m column maintained isothermally at 50
deg.C. On maximum sensitivity only one minor multiple peak
of retention time 0.50 seconds was noted. This was
identified by GC/MS as air with a trace amount of propane.
4 .
- 59 -
Solvent Adsorption Sample
The 200mL volume of dichloromethane solvent was reduced
to 100 microlitres by careful evaporation under a stream of
dry nitrogen. Water traces were removed by passing the
liquid through a small column of anhydrous sodium sulphate,
and samples were stored in small volume glass vials with
Teflon seals. An equivalent volume of the distilled
dichloromethane was treated in a similar manner to provide a
blank. Injection of 1.0 microlitre portions of sample onto
the Dexil 300 packed column, described above, gave a GC
trace with a large solvent peak with a number of shoulder
peaks. Trace amounts of other compounds were observed,
however the blank solvent run provided a very similar trace,
indicating the presence of solvent impurities. A high
resolution 55m OV101 SCOT colUmn was installed in the GC
mass spectrometer system to enable separation and, where
possible, identification of the components. 0.5 microlitre
of sample was injected onto the column in a Grob type
injection at ambient temperature. Temperature programming
was commenced at 50 deg.C. Details of operating conditions
are set out in Table VII.
- 60 -
Gas chromatograph: Pye series 204 Column: OV101 SCOT 55m glass 0.5mm dia Carried gas: He at 1.0 mL/min. Temperatures(deg.C): Inlet 225, outlet 250, interface 250 Oven programme: Ambient, then 50 deg. to 200 deg,
2 deg/min to scan 375 then 8 deg/min. Mass Spectrometer: VG Micromass 7070F
Scan rate 1 per 2.5 seconds. Energy 70Ev.' Data System: VG 2235 using a PDP 8/A620 minicomputer.
Table VII. GC/MS Operating Conditions
Identification was made by comparison of mass spectral
data in the literature [193], and the library of authentic
samples stored in the data system, and also on the basis of
retention time data. Additional information was gained from
the fact that OV101 is a relatively non-polar phase and
separates most components on a boiling point basis. The
trace obtained from the solvent run is shown in Figure XVI
and the component identities in Table VIII.
1 483157
tetrachloroethyle
ne 9.
chloroform 3.
• a IVO ZOO 228 480 423.21 01 0 111 8.1 1210 . 1C.3 ZOI1 Z3.0 7V0 r7:
tric
hlo
roethylene 6.
1 8
dichlorome
thane 1.
tric
hloroethane 4.
C.N1
00 L. C 00
"OW
37
-61 -
Figure XVI. TIC Trace Dichloromethane Blank OV101 Capillary Col. 50-200 deg. C. (Conditions as per Table VII.)
Peak No. Scan No. Identity
1 75-90 dichloromethane 2 97 dichloroethylene 3 121 chloroform 4 143 1,1,1 trichloroethane 5 162 cyclohexane 6 188 trichloroethylene 7 234 4 methyl 2 pentanone 8 276 toluene 9 352 tetrachloroethylene
10 432 ethyl benzene 11 444 xylene
Table VIII. Components Identified in Dichloromethane Solvent Blank
0
0 _c
1,1,
1 t
ric
hlo
roe
t han
e 4.
1SS
chlo
rofo
rm 3
.
13
' 1363315
La
hep
tan
al is
om
er 1
7.
1 2.40 288 3:i2 11:13
r 228 Z 488 440 488 17:S8 14:88 isto - 2711-5 13:13
- 62 -
o af,,,--,--77"-77-NT i1 1---T----1 — I-- 0 1-0 m Ira iss zem
0:2 1:33 2315 4:52 clas 87
Figure XVII. TIC Trace of Solvent Trap Volatiles OV101 Capillary Col.. Conditions as per Table VII.
Peak No. Scan No. Identity
1 74-88 dichloromethane*
2 93 dichloroethylene*
3 117 chloroform*
4 139 1,1,1 trichloroethane*
5 150 benzene
6 159 cyclohexane*
7 177 1,2 dichloropropane
8 185 trichloroethylene*
9 228 4 methyl 2 pentanone*
10 258 toluene*
11 284 4 methyl pentanal (?)
12 296 tetrachloroethylene*
13 332 ethyl benzene*
14 337 )
15 350 ) 0,m and p xylene*
16 362 )
17 378 heptanal isomer
18 404 octanal
19 411 n-decane
Table IX. Components Identified in Solvent Trap Concentrate.
Injection of the same quantity of sample from the
-63 -
solvent trap under similar conditions gave the total ion
current trace shown in Figure XVII. Initial oven
temperature conditions caused a shortening of retention
times and hence the peak scan numbers are not identical to
those in Figure XVI. Components identified are shown in
Table IX with peaks also found in the solvent marked with an
asterisk *• High concentrations of dichloromethane and
tetrachloroethylene caused overloading of the MS system and
temporary shutdown of the beam as shown by the return of the
trace to baseline.
c) Cryogenic Trap Sample
The dichloromethane washing from the cryogenic trap
sample also contained a considerable amount of water, was
passed through an anhydrous sodium sulphate column and then
evaporated to 200 microlitres, as described above. The GC
and total ion current traces were virtually identical to the
dichloromethane solvent blank traces. No other compounds
were detected.
d) Tenax Trap
The Tenax sample trap was removed from the stoppered
glass carrying tube and placed into the thermal desorption
apparatus, flushed with carrier gas and the system coupled
to the GC/MS. A 10 minute thermal desorption time at 300
deg.0 was used. The total ion current trace is shown in
Figure XVIII the components are identified in Table X, and
the mass spectra are listed in the appendix. •
14
I I
03
! 13
go
I
I I
• -
--n
acet
oncm
____
tin
ethy
lene
on
ch
lori
de 5
. ca
rbon
dio
xide
7.
n entane meth 1 entane 8
chlo
ro-
form
9.
I benzene 10.-
4-4
•
chloroform 11.
,y
00
acrole
in
aceto
ne
tolu
ene 12.
w te
trachloroethylene 13.
•0
)
CD
••
mono
terpene 14.
phenol
15
n-pe
ntan
e
o.m.
p. c
reso
l 16
. 17
. 18
.
ethy
l ph
enol
19.
dime
thyl
phe
nol
20.
2 et
hyl
phen
ol 2
1. •
n pentadecane 22.
mlhe
ptad
ecan
e 21
.
-65-
Peak No. Scan No.
1 20 2 23 3 24 4 28 5 29 6 32 7 50 8 70 9 75
10 114 11 119 12 245 13 302 14 402 15 438 16 460 17 469 18 476 19 490 20 495 21 502 22 610 23 642
Identity
Hydrocarbon (pentadiene) acrolein + pentadiene isomer + acetone acetone methylene chloride + acetone + unknown methylene chloride Freon carbon dioxide n-pentane + methyl pentane chloroform benzene chloroform toluene tetrachloroethylene unknown monoterpene phenol
) ) o,m and p cresol
) ethyl phenol dimethyl phenol 2 ethyl phenol pentadecane unknown
Table X. Components Identified in Tenax Trap.
High concentrations of contamination adsorbed from the
solvent traps tended to mask some of the earlier peaks,
however, acrolein, acetone , a number of phenols and cresols
were detected. A plot of the 27 and 56 mass ions in the
first 100 scans shows the presence of a suspected acrolein
peak in the early section of the trace - Figure XIXa. The
characteristic ions 27 and 56 maximise at scan number 23
under the leading edge of the acetone peak, this information
coupled with the coincident retention time of acrolein
confirmed the presence of the substance.
- 66 -
B.Discussion.
The problems associated with the various trapping
methods, as outlined in the literature sources, were shown
to be considerable in this attempt at collecting a trace
component in an industrial process. Solvent contamination
and escape proved to influence each determination. Trapping
efficiency of the unknown component in the direct headspace
collection, the solvent trap, and the cryogenic trap, proved
to be too low, or the losses during concentration too high,
that instrumental methods failed to detect the substance.
This was in spite of the fact that the substance was
painfully obvious to the eyes and nose.
Components detected in the solvent trap extract could
not account for the observed effects in the concentrations
measured. The components present could be explained as
either solvent impurities, products from the furnace or
breakdown products of the insulation.
Acrolein (propenal), detected in the Tenax trap at a
concentration -of approximately 1 part per million, has a
toxic dose level (TDL) OF 0.1 PPM [194], and the boiling
point of 52.7 deg.0 correlates with the elution from the GC
column just prior to acetone (bp 56.2 deg.C). A small
quantity of acrolein was manufactured synthetically and
collected along with some of the industrially generated
material. The two substances co-eluted from the GC column
and gave identical mass spectra. (Figure XIXb.) The
physiological effects of the synthetically produced acrolein
- 67 -
were identical to the gaseous product from the furnace; to
this point some difficulty was experienced in convincing the
industrial operators that the active constituent was present
in relatively low concentrations.
A search was conducted of the stored spectra from the
solvent and cryogenic trap runs but acrolein and several of
the other low boiling components could not be detected.
Apparently the evaporation of the solvent and the drying
step has removed the lower boiling point components.
Literature sources describe a number of ways in which
acrolein may be produced, from oxidation of petroleum gas
[195], as a by-product from pyrolysis of paints and
degreasing solutions and from the heating of plastic tubing,
insulation and metal foil tape [196]. Two main sources of
the acrolein would therefore appear possible.
i. from oxidation of the L.P. fuel gas ii. from pyrolysis of the furnace construction/insulation
material.
- 68 -
CD
SS
SO
Figure XIXb. Mass Spectrum of Acrolein (propenal).
- 69 -
C.Summary and Conclusions.
Four trapping techniques were used in order to determine
the nature of an air contaminant in the vicinity of an
industrial furnace. Direct headspace injection provided
little useful information as the ambient concentration of
the contaminant was below the instrument detection level.
Solvent trapping and cryogenic concentration did not provide
sufficient quantity of the unknown contaminant, free from
solvent interferences, to give positive identification.
Major losses of the highly volatile unknown compound
occurred during the removal of solvent and/or water, and
this problem coupled with the low concentration present,
made identification difficult with the more classical
techniques.
Tenax trapping of the component from the air allowed
qualitative and approximate quantitative determination of
acrolein in the hot gas stream from the furnace. Acrolein
was confirmed using a synthetically produced compound as a
comparison. Follow-up work using the more polar Chromosorb
104 as a trapping medium also confirmed the presence of
acrolein at the lppm level.
The source of the acrolein was either:
i) incorrect combustion conditions of the L.P. flame.
ii) a pyrolysis by-product of the furnace construction/ insulation material.
- 70-
CHAPTER V.
VOLATILE COMPONENTS OF SOME NATIVE PLANTS.
Introduction.
A need exists to examine systematically the chemical
composition of the essential oils of Australian native
plants. Work on the Eucalyptus genus has been conducted by
Penfold and Morrison [197], Hellyer and McKern [198] and
others at the Museum of Applied Arts and Sciences in New
South Wales. McKern [202] has reviewed some of the history
of essential oil studies in Australia, and has also reviewed
[203] the problems associated with attempts to utilize
chemical compositions of volatile oils in taxonomy. General
reviews of work on alkaloids and terpenes are published by
the Royal Society of Chemistry [204,205]. Investigations of
the alkaloids of native plants has been conducted by Bick et
al [206], and of terpene composition by Ayling [207].
A number of Tasmanian plants have volatile components
that impart attractive odour or taste properties. Two of
these, Drimys lanceolata and Prostanthera lasianthos, are
examined in this work, with the object of documenting the
steam distillate oil and of developing techniques for the
characterisation of small quantities of volatile organic
compounds. The third section examines the relationship
between the volatile components of Boronia meciastigma, a
native plant of Western Australia.
-71 -
A. Components of the Steam Volatile Oil of
Drimys lanceolata.
Introduction.
Drimys lanceolata occurs in the Tasmanian highlands and
also in Victoria and New South Wales. Commonly called
'Mountain Pepper' due to the very 'hot' peppery taste of the •
leaves, the plant is widely distributed in Tasmania. Plants
on high windswept plateaus and exposted ridges tend to be
short and flattened in appearance, whereas, in gullies the
growth tends to resemble small trees or tall shrubs. The
height varies from 0.2m to 5.0m and the young stems are
crimson in colour [208].
Previous experimental work on extracts from the plant
were conducted by Stevens [209], and Loder [210], and work
on the related New Zealand plant, Pseudowintera colorata,
was performed by Corbett and Grant [211].
A preliminary investigation of the steam distillate of
Tasmanian samples of Drimys lanceolata by Stevens indicated
that there existed considerable variations in physical and
chemical properties of oils derived from plants found in
separated areas of the state. The sesquiterpene alcohol
guaiol was found to crystallize from two of the oils.
Loder [206] used a hexane extraction method to isolate
two crystalline components from the leaves, Rolygodial
(0.26%) and guaiol (0.035%). Polygodial was described as
- 72 -
partly responsible for the pungent taste of the leaf.
Corbett and Grant listed a number of components derived from
column distillation of the volatile oil from Pseudowintera
colorata (Maori Pepper). The fractions and percentage
composition are listed in the discussion section.
The composition of the volatile leaf oil components of
Drimys lanceolata has apparently not been reported in the
literature. Samples of the plant were collected from a
number of areas of Tasmania to determine whether significant
compositional variations occured.
1) Experimental
a) Sample Collection
Small branches and leaves were collected from five
scattered areas of Tasmania. Samples of the plant collected
adjacent to the Mt. Wellington park differed from the others
in that the height of plant was relatively small (0.25m).
The other samples were collected from small trees or shrubs
growing in sheltered valley situations in deeper soil.
b) Distillation
The leaves were stripped from the branches and the steam
volatile components were passed through a vertical glass
column packed with 5mm lengths of glass tube and condensed
before collection in a saturated aqueous sodium chloride
solution. The oil was separated from the aqueous solution by
decantation and triple extraction with diethyl ether. Ether
- 73-
was removed by low temperature evaporation using a dry
nitrogen gas stream. Residual water was removed by passing
the oil through a small column of granular anhydrous sodium
sulphate. Percentage yield and some physical properties of
the volatile oil are recorded in Table XI.
Sample Plant Oil Area Height(m) Yield (%) Density(g/mL)
Mt. Wellington 0.25 0.37 0.901
Parrawe 2.5 0.70 0.910
Mt. Field 2.5 0.43 0.917
Moogara 1.5 0.50 0.920 Wtern Tiers 2.0 0.35 0.928
Table XI. Average Percentage Yield and Physical Properties of the Steam Distillate of Drimvs lanceolata.
c) Analytical Results
Identification of components in the steam distillate was
carried out by comparison of GC retention times on two
columns and mass spectral data. The result for each
district is derived from a composite of the oil from three
trees.
The GC traces are shown in Figures XX - XXIV. Relative
retention indices were caculated from separate and -
coinjected mixtures of C10 to C22 n-alkane hydrocarbon
standards at a concentration of 0.040 percent each in
chloroform. Reproducability of the coinjected mixture was
generally excellent on the OV101 capillary GC column;
however, some variations occured on the Carbowax 20M column
compared with the literature values [212]. Retention times
and peak areas were recorded on a Shimadzu Chromatopac-E1A
- 74-
and the percentage composition of each component calculated
on the basis of the peak areas.
The GC/MS total ion current traces (Figures XXVI,XXVII)
were obtained on the VG instrument previously described,
using a 50m CW2OM silica capillary GC column (Figure XXVII),
and a similar OV101 column (Figure XXVI); temperature
programmed at 4 deg.C/min. from 80 to 200 deg. C. Individual
component mass spectra are listed in the appendix at the end
of the thesis.
The peak scan numbers and component identities of the
more complex Moogara sample are listed in Table XII.
_ I A---
1 0
i_
.
0 0 -
._
19
•
.
24 .
CD
.
._ (D 7
35..
1 r
.
.
i
15
- 75-
Time (mins)
Figure XX. GC Trace D. lanceolata on CW2OM Capillary Col. 50-200 deg. C at 2 deg./min. Sample ex Moogara. Component Identification Table XII.
Time (mins) -4-
Figure XXI. GC Trace D. lanceolata on CW2OM Capillary Col. 50-200 deg. C at 4 deg./min. Sample ex Parrawe. Component Identification Table XIII.
Fl D
Resp
ons
e ÷
15
3 9
21 2-
36
3 0
22
15 2 4
2 5
26
36 30
1 k_
Time (mins)
F I D
Resp
o nse
+
- 76 -
Time (mins)
Figure XXII. GC Trace D. lanceolata on OV101 Capillary Col. 50-200 deg. C at 4 deg./min. Sample ex Wtern Tiers.
Component Identification Table XIII.
Figure XXIII. GC Trace D. lanceolata on CW2OM Capillary Col. 50-200 deg. C at 4 deg./min. Sample ex Mt Field. Component Identification Table XIII.
F I D
Rep
onse
±
- 77 -
15 24
36
313
,
Time (mins) -4-
Figure XXIV. GC Trace D. lanceolata OV101 Capillary Col. 50-200 deg. C at 4 deg./min. Sample ex Mt Wellington.
Component Identification Table XIII.
CO7
•-■
63- 1 i.
100 200
----r16llie - XXV.- 6-614&1' Mass Spectrum of - Guatol ex Wtern Tiers.
FID
Res
ponse
-+
S8 1 476
S00 2510
1000 31125
— ...... GOO 113:S1
r- .030
G:17 12:34
31.33 00 000
1S.40
- 78 -
0.1
Figure XXVI. TIC Trace D. lanceolata ex Wtern Tiers. OV101 Capillary Col. 80-200 deg. C; 4 deg./min. Component Identification Table . XIII.
Figure XXVII. TIC Trace D. lanceolata ex Moogara. CW2OM Capillary Col. 80-200 deg. C; 4 deg./min. Component Identification Table XII.
cs*., cr.)
163360
99
352
140
- 79-
Peak Scan Retention Percent Identity No. No. Index Composition
solvent (chloroform) ,c-pinene /s-pinene myrcene -ic-phellandrene limonene /3- phellandrene 1,8 cineole monoterpene (?) p cymene unknown X (base 68) isomer of X isomer of X cubene
unknown bourbonene
unknown unknown (X + CH2) linalool caryophyllene terpinene-4-ol sesquiterpene monoterpene alcohol
-,c-terpineol sesquiterpene piperitone cadinene ( ?) cadina 1,4 diene calamanine farnesol unknown methyl eugenol (type) sesquiterpene alcohol sesquiterpene alcohol guaiol oxygenated sesquiterp. eugenol isomeric guaiol (?) unknown methyl eugenol + CH2 unknown unknown myristicine (?) unknown others
Table XII. Identification Details of Steam Volatile Oil of Drimys lanceolata ex Moogara.
1 96 - - 2 98 1039 7.8 3 116 1124 3.6 4 127 1156 1.5 5 130 1177 0.3 6 141 1206 1.9 7 145 1218 0.1 8 148 1228 18.8 9 158 1246 0.1
10 170 1272 0.4 11 206 1328 0.3 12 224 1351 0.4 13 268 1402 0.1 14 279 1420 0.3 15 304 1448 0.1 16 325 1482 . 0.1 17 332 1494 0.1 18 342 1501 0.3 19 353 1506 38.8 20 386 1617 0.4 21 395 1628 0.4 22 435 1648 0.4 23 455 1655 0.1 24 476 1661 3.4 25 481 1702 0.2 26 503 1739 0.3 27 516 1758 0.8 28 537 1782 0.1 29 581 1842 3.6 30 605 1875 0.1 31 666 1938 0.2 32 738 2044 0.1 33 771 2046 0.2 34 779 2049 0.2 35 801 2058 8.8 36 826 2078 0.4 37 858 2103 0.4 38 861 2112 0.3 39 874 2122 0.1 40 885 2132 0.3 41 905 2154 0.1 42 910 2158 0.3 43 929 2172 0.5 44 1015 2208 0.1
3.2
- 80 -
Peak Component No
Mt. Parrawe Wellington
Mt. Field
Western Tiers
2 .0c-pinene 10.2 5.4 5.1 6.5 3 /3-pinene 11.2 1.3 4.6 8.1 4 Qc-phellandrene 3.1 3.9 5.8 0.7
• 5 myrcene 0.6 0.2 1.6 3.7 6 /3-phellandrene 0.4 0.1 0.1 ) 7 heptanone 0.1 0.1 0.1 ) 1.0 8 limonene 0.1 0.7 5.7 0.6 9 1,8 cineole 2.6 0.5 11.2 7.6
10 monoterpene 0.1 0.1 1.1 0.1 11 p-cymene 0.2 1.1 1.9 0.3 12 /3-ocimene or,
A-3 carene 0.1 0.1 0.1 0.8 13 terpinolene 0.6 0.3 0.7 0.2 14 unknown 0.4 0.1 0.1 0.3 15 linalool 31.8 40.7 18.8 17.2 16 monoterp. acetate 1.2 0.3 0.1 0.1 17 caryophyllene 0.1 ) 0.1 0.1 18 terpinen-4-ol 0.7 ) 2.9 0.4 0.9 19 .-terpineol 4.1 0.9 0.8 2.3 20 sesquiterpene 0.3 0.1 - - 21 piperitone 0.1 0.9 7.0 3.4 22 safrole 0.1 0.2 1.1 1.7 23 unknown 2.7 0.1 0.8 0.3 24 eugenol 8.6 5.7 10.0 5.5 25 methyl eugenol 1.6 0.9 1.3 0.7 26 unknown 0.3 0.2 1.1 0.1 27 unknown 0.2 0.6 0.1 0.3 28 geranial 0.5 0.4 0.4 0.1 29 unknown 0.2 2.4 1.1 0.5 30 myristicine 1.2 5.7 5.0 5.1 31 /g-cedrene(?) 0.1 0.1 0.1 0.1 32 x-murolene(?) 0.1 1.4 1.7 0.3 33 mycenol or )
elemol ) 0.2 0.9 2.2 1.1 34 /3-farnesene(?) 0.1 3.1 0.9 0.3 35 dihydrocarvyl
acetate(?) 0.9 1.8 0.6 1.3 36 guaiol 4.3 8.0 1.6 16.5
Others 10.8 13.0 6.7 12.2
Table XIII. Percentage Composition Drimys lanceolata From Various Areas of Tasmania.
The percentage composition of the oil samples from the
other areas of the state are shown in Table XIII.
A number of components were not identified due to the
-81 -
lack of comparative data in the literature, and the lack of
time available to prepare pure standard samples from the
crude oil on a preparative scale.Characterisation of minor
components would require the collection of large quantities
of leaf material as the percentage of oil present is
relatively low.
ii) Discussion
Variation in the percentage composition of the main
components: linalool, -e-pinene,/1 -pinene, 1,8 cineole,
guaiol, was considerable (up to three times for each
component) between areas. The sample taken from Moogara
varied in composition from the other sites in that the oil
contained a number of components that were not present in
significant concentrations in samples collected in the other
areas. The presence of a component with a similar mass
spectrum to guaiol was of particular interest (mass spectra
from Scan No. 861 compared with Figure XXV). Unfortunately
there was insufficient material to isolate and confirm the
structure of this component.
The similarity in composition of the Tasmanian plant to
that of New Zealand Pseudowintera colorata is shown by the
components from this plant listed in Table XIV.
-82 -
Fraction % Composition Components 1 1.0 ,..e-pinene, -1n-thujene 2 1.0 /3-pinene 3 0.5 myrcene 4 0.5 carbonyl cpd 5 2.25 limonene, dipentene,Qe -terpinene 6 2.25 /g-phellandrene mixture 7 1.0 terpene alcohol (C io HnO) 8 - carbonyl cpd (0 10 H u+ 0) 9 1.0 --e-terpinene
10 1.0 terpinolene,,4 7-cymene 11 0.5 ester 12 0.5 alcohol (CO 34 0) 13 1.0 alcohol (C,
0 H.,0 0) .
14 0.5 hexenyl yalerate 15 1.0 eugenol 16 16.5 bicyclic sesquiterpene 17 1.0 bicyclic sesquiterpene 18 1.0 aromadendren 19 1.0 humulene 20,21 4.5 alcohol unknowns 22 3.0 aromatic hydrocarbon 23 4.5 alcohol 24 2.0 sesquiterpene ketone (C,5 Hz.t 0)
Residue 52.0 tricosane, pentacosane and sesquiterpene ketone
Table XIV. Percentage Composition of Steam Distillate of Pseudowintera colorata [211].
A considerable amount of additional experimental work is
required to enable a final characterisation and confirmation
of the identity of the remaining components of the steam
distillate of the oil of Drimys lanceolata. Techniques such
as GC Fourier transform infrared analysis, as well as
laser-Raman and UV methods, for determining functional
groups and molecular structure would assist in the complete
characterisation of the oil.
- 83 -
B. Components of the Steam Volatile Oil of
Prostanthera lasianthos.
Introduction.
Prostanthera lasianthos occurs in Tasmania, Victoria and
New South Wales on the margins of wet eucalypt forests. The
shrub or small tree grows to a height of from 2 to 6m [208].
The strong-smelling flowers are formed in December to
January, hence the common names of Christmas Bush (or Mint
Tree).
The terpene composition of the steam volatile oil of the
related Prostanthera rotundifolia has been reported by
Ayling [207] but there was no indication in the literature
of previous experimental work being performed on P.
lasianthos.
1) Experimental
(a) Sample Collection
Leaves were collected in April from four trees growing
in small valleys draining to Pirates Bay on Tasman
Peninsula. The leaves were concentrated on the extreme
outer ends of the branches and were somewhat low in numbers
due to heavy growth of surrounding plants. Height of the
trees were 3 to 4m.
- 84 -
(b) Distillation
The procedure followed for distillation of the leaf oil
was as described in Section A for D. lanceolata. Percentage
yield (by weight) of the steam distilled oil derived from a
composite of the leaves from the four trees was 0.12.
(c) Analytical Results
50m silica capillary GC columns were used to
separate components in the oil and their mass spectra
recorded. The total ion current trace (Figure XXVII) was
obtained by injecting 0.4 microliters of the oil (with a
10:1 split), into the GC/MS using a CW2OM GC column
temperature programmed from 50 to 210 deg.0 at 4 deg./min.
to separate and characterise the peaks. Component
identification was based on relative retention index and
mass spectral data. The component mass spectra from two
GC/MS runs are shown in detail in the appendix. DE1036
(Figure XXVIII) shows the total ion current trace from the
OV101 silica capillary GC column with a similar loading to
the CW2OM column but temperature programmed from 50 to 240
deg.0 at 4 deg./min. Scan numbers and tentative MS
identification data are recorded in Table XV, and the
component mass spectra are listed in the appendix.-
The n-hydrocarbon standards peaks are shown in the
temperature programmed GC trace of Figure XXIX. Table XVI
lists the standards and the temperature programmed retention
times used to calculate the retention indices obtained on a
- 85 -
50m OV101 glass SCOT capillary column. The same column
under identical programming conditions was used to obtain
the GC trace of Figure XXX. The retention indices of the
recorded peaks, the literature values and the percentage
composition are tabulated in Table XVII.
377
71060
254
7B
296
47
- 86 -
CRL: 11)550 16628
72
85
7?1
631
4 581
147 9 2
9:1 G137 E:80 19.58
008 2.8126
imm 17113 Scan No 23:2 83:28 Time
Figure XVII. TIC Trace P. lasianthos CW2OM Capillary Col. 50-210 deg. C at 4 deg./min. Component Identification Table XV.
280 408 288 21% 2:i0 12:2C 18:53
880 2Ss I) Izo8 Scan No. 11/.4s
Time
Figure XVIII. TIC Trace P. lasianthos OV101 Capillary Col. 50-240 deg. C at 4 deg./min. Component Identification Table XV.
- 87 -
60 70
C9
C10
C11 C17 C3 C12 C16 C14 C15 F
ID R
esp
onse
.
C20 C18 C19
20 40 Erne (mins.) . .
Figure XXIX. GC Trace n-hydrocarbon Standards. Conditions as Shown Below.
Standard Retention Time (minutes)
Retention Index
n-C9 8.55 900 n-C10 13.50 1,000 n-C11 19.53 1,100 n-C12 25.95 1,200 n-C13 32.36 1,300 n-C14 38.56 1,400 n-C15 44.51 1,500 n-C16 50.20 1,600 n-C17 55.61 1,700 n-C18 60.81 1,800' n-C19 65.78 1,900 n-C20 70.58 2,000 n-C21 75.69 2,100
Table XVI. Retention Times and Indices for n-hydrocarbon Standards on OV101 Glass Capillary Column 50-220 deg.0 at 2 deg./min.
- 88 -
14
33 47
32
28
19
8
10 20 30 40 50 60 70 80 85 Time (nuns.) --
Figure XXX. GC Trace P. lasianthos OV101 Capillary Col. 50-220 deg. C at 2 deg./min. Component Identification Table-XV.
- 89 -
Scan No. Scan No. Peak
CW2OM OV101
No. Tentative Identification
1 2 3 4 5 6 7 8 9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49
85 78 123
153-189 243 250
( 254 146-180 ( 267
( 296 ( 309
327 304,319 331 258
344 292 377
394 423 484
404 511
420 581
437 458 460 492
594
499 505
693 514 608 617 631
532 658 677 691 721
548 735
890, 852
584 593-603
741 742 796 801-832 833
655 1123
670 714-765
845 857-976
978 992
1002 1052
1019
Table XV
solvent 4 methyl-pent-1-en-3-one unknown pentyl ester benzaldehyde
-pinene camphene /5 -pinene myrcene < -phellandrene cymene mixture limonene 1,8 cineole + cymene 1,8 cineole unknown momoterpene trans hex-3-enol cis linalool epoxide trans linalool epoxide linalool unknown unknown camphene hydrate pinocarvone unknown archillinol (?) fenchone (?)
caryophyllene terpinene-4-cd sesquiterpene (farnesene?) unknown unknown mixture ..6-terpineol .-selinene 4 phenyl butan-2-one carvone unknowns unknown
elemene myrtenol unknown carveol iso-bornyl acetate thymol unknowns p-cymene-8-ol unknowns unknown ledol /3-eudesmol
Component Scan Numbers and Tentative MS Identification of Prostanthera lasianthos Oil Components.
- 90 -
Peak Rel.Ret. Rel.Ret. Percent
No. Index Index Composition (Lit.) (Calc.)
1
Component Identity
solvent 2 0.1 4 methyl-pent-1-en-3-one 3 1.3 unknowns 4 0.1 pentyl ester 5 947 0.2 benzaldehyde 6 942 930 3.2 .4:-pinene 7 954 941 0.8 camphene 8 . 981 968 1.8 /3- pinene 9 986 987 0.5 myrcene
10 1002 996 0.7 ,?< - phel 1 andrene 11 1020 ) cymeme mixture 12 1030 ) 1024 22.6 limonene 13 ) 1,8 cineole + cymene 14 1027 ) 1,8 cineole 15 0.1 unknown 16 0.1 trans'hex-3-eno1 17 1068 0.1 cis linalool epoxide 18 1082 1080 0.2 trans linalool epoxide 19 1092 1093 2.1 linalool 20 1101 0.1 unknown 21 1107 0.1 unknown 22 1111 0.2 camphene hydrate 23 1125 2.4 pinocarvone 24 1138 1.1 unknown 25 1152 1.6 archillinol 26 1080 0.3 fenchone ? 27 1428? 1351 0.2 caryophyllene ? 28 1175 1165 3.2 terpinene-4-ol 29 1447 0.2 sesquiterpene (farnesene?) 30 1467 0.1 unknown 31 0.3 unknown mixture 32 1185 1180 3.8 *Ia-terpineol 33 1494 3.9 /s-selinene 34 1502 1.8 4 phenyl butan-2-one 35 1228 0.4 carvone 36 1.7 unknowns 37 0.2 unknown 38 0.8 ).-elemene 39 0.4 myrtenol 40 0.4 unknowns 41 0.7 carved] 42 1279 1275 0.2 iso-bornyl acetate 43 1287 1.3 thymol 44 0.3 unknowns 45 1.1 p-cymene-8-ol 46 3.7 unknowns 47 1581 3.4 unknown 48 1623 1.4 ledol 49 1728 1.9 /3 -eudesmol
28.9 other Table XVII. Component Identification by Retention Index
(on OV101) and Approximate Percentage Composition Prostanthera lasianthos.
- 91 -
ii) Discussion
The use of retention indices to assist in the
identification of components in complex mixtures has been
widely reported in the literature [213, 214].
Identification of a well resolved component in a GC run is
relatively straight forward if the component retention time
has been accurately measured previously and the run is
reproduceable. Problems are encountered when the peak is
not well resolved or, if the component has not been
previously measured. Tables provided in the literature
[212] are often of assistance but must be used with caution.
Polar phases, such as Carbowax, can readily alter in
characteristics as the column ages. Components that eluted
in the order a,b,c,d,e can alter and elute a,b,d,e after a
certain amount of the liquid phase has been stripped from
the column with either repeated injections of solvent, or
high temperatures.
The presence of a large number of components with
similar boiling points made baseline separation and
quantitation difficult. Hence, quantitation of components
by area integration proved to be somewhat inexact. Main
components were 1,8 cineole and a mixture of cymenes, obc-
pinene,.4-terpineol, terpinene-4-olOselinene and an unknown
compound with a molecular weight of 220. A relatively high
proportion of the unknowns were oxygenated sesquiterpene
compounds that would contribute to the aroma characteristics
of the oil. Preliminary separation of the compounds into
-92-
terpene hydrocarbons and oxygenated classes would assist in
clarifying the GC trace and allow greater accuracy in
quantitation of components.
Ayling [207] examined the steam volatile oil of the
related Prostanthera rotundifolia. A comparison of the
composition of the main components of this oil with
Prostanthera lasianthos is given in the following table.
Component
.04 -pinene
P. lasianthos P. rotundifolia [207]
3.2 1.4 camphene 0.8 0.1
-pinene 1.8 2.3 myrcene 0.5 ) 'le -phellandrene 0.7 ) 3.7 limonene ) 1.1 1,8 cineole ) 22.6 47.0 p-cymene -. 23.2
terpinen-4-ol 3.2 1.5 cic -terpineol 3.8 4.1 terpene alcohol 1.1 6.9 other 62.3 8.7
Table XVIII. Comparison of the Percentage Composition of Prostanthera lasianthos and P. rotundifolia.
1,8 cineole is the major component in both oils and many
of the minor components are present in somewhat similar
concentrations. Large differences are however apparent in
the higher boiling components of the oils.
iii) Conclusions.
Examination of the steam volatile oils of D. lanceolata
and P. lasianthos provided the opportunity to develop
retention index and mass spectral techniques applicable to
volatile components. The advantages of fine bore silica
capillary columns and the introduction of the 'end of the
- 93 -
column through to the ion source of the mass spectrometer
were proved using the steam volatile oils.
- 94 -
C. Volatile Components of Roronia megastiqma.
Introduction.
The essential oil industry in Tasmania has developed
gradually over the last few decades into a relatively small
but viable agricultural/processing industry. Recent
, research within the Agricultural SciencelFaculty __I of the
University has indicated that a number of groups of plants
produce high quality essential oils when grown in selected
areas of Tasmania [215].
The determination of the optimum time for picking the
leaves or flowers of a crop is an important factor in the
production of a high quality oil. Collection of the
volatile compounds from the surrounding air and rapid
analysis for critical components may provide a viable
alternative to the normal steam distillation procedure. The
collection of headspace air samples has a number of
advantages in that it provides a non-destructive collection
method and under most conditions an inbuilt averaging system
as the sample collection tube can be moved from one area of
a field or glasshouse to another. An automated variation of
this collection-analysis system would provide rapid
analytical results for the harvester.
Commercial processing of amniA_EllegAatizo involves
extraction of the soluble components by solvent and the
production of a 'concrete' consisting of volatiles and
higher molecular weight substances [216]. The objective of
- 95 -
the work described below was to compare the headspace
components trapped from the flowers, the headspace above the
concrete and the components present_in the concrete.
i) Experimental
a) Sample Collection
Boronia flowers (Boronia megastiqma) were provided by
Mr. G. Leggett from the Agricultural Science Faculty.
Samples of the headspace above the flowers were obtained by
placing the flowers (163), in a clean glass jar (previously
baked at 500 deg.C) and drawing the volatiles into a Tenax
sample collection tube at 40 mL per minute for 15 minutes.
The flowers were then extracted with petroleum ether and
the solvent was evaporated by warming the solution and
blowing a stream of dry nitrogen over the surface. The
larger portion of the resulting waxy residue - concrete -
was then heated to its softening temperature (45 deg.C) by
immersing the glass container in a water-bath. Headspace
from the concrete was collected using a second Tenax tube
under similar conditions to the first sample. A portion of
the concrete was directly injected into the GC/MS system for
comparison with the headspace volatiles.
b) Anablitical Results
' Separation of components was achieved using a 50m glass
OV101 SCOT capillary GC column. Components were identified
by mass spectral information verified by comparison with
- 96 -
library spectra of authentic compounds from previous work
[215], and by retention times. Individual mass spectra are
presented in the appendix.
Gas chromatographic conditions are described in
Table XIX, and component identification in Table XX.
Concrete Concrete Headspace
Flower Head space
Designation AG110-AG113 DEBRO4 DEBROO Collection Temp.(deg.C) 45 20 Injection In Solvent Splitless Splitless Initial GC Temp. 80 30 30 Final GC Temp. 250 200 200 Carrier Gas He He He
Flow Rate (mL/min) 1.0 1.5 1.5 Inlet Temp. 200 200 200 Outlet Temp. 250 250 250 Temp.Prog.Rate (deg.C/min) 4 3 3
Table XIX. Gas Chromatography Conditions for Boronia megastigma.
3.
1.2 B
18.
6 152 ZS 21 SI h78 gr3 141Mk
8.8
19S3
1 2
Figure XXXI. TIC Trace Headspace of Boronia megasticima Flowers. OV101 Capillary Col. Peak Identification Table XX. _
- 97 -
(1)
Figure XXXII. TIC Trace Headspace of Boronia meciasticima Concrete. Collected by Tenax Sample Tube. OV101 Capillary Col. Peak Identification Table XX.
/so 8CAN MITER 23.14 Ret. Time (m 0.1
- 98 -
Figure XXXIII. TIC Trace of Concrete of Boronia megasticima [215]. OV101 Capillary Col. Peak Identification Table XX.
- 99 -
Peak Component No.
Code:
Concrete
Ag
Scan Number Concrete
Headspace DEBRO4
Flower Headspace DEBROO
la. Unknown monoterpene 8 340 1. -4-pinene 34 372 628
2. camphene 46 387 642
3. /3 -pinene 392 691 4. mycrene 72 399 710
5. limonene 112 418 759
7. linalool 151 462 nd
8. methone 224 574 802 8a. naphthalene 600
8b. Unknown aromatic cpd. 604 8c. Unknown C12H16 (?) 688 9. methyl naphthalene 375 705
10. methyl N decanoate 404 736 13. ethyl decanoate 478 nd 17. dodecanol 564 nd
18. /S-ionone 572 858 1024 20. dihydroactinidiolide 883 1260
22. dodecyl acetate 698 1296
26,27. heptadecane 765 1366
Table XX. Peak Identification and Mass Spectra Scan Numbers for Boronia megasticima.
nd = not detected
The total ion current traces of the three samples of
volatiles are shown in Figures XXXI to XXXIII.
A comparison of the relative proportions of the
.components is given in Table XXI.
- 100 -
Peak Component No.
Concrete Concrete Headspace
Flower Headspace
la. Unknown monoterpene. 0.8 0.9 3.5 1. ..f-pinene 1.6 3.1 26 2. camphene 0.5 0.9 26 3. /3-pinene 0.3 0.9 32 4. myrcene 0.5 0.4 3.1 5. limonene 2.6 1.8 3.8 7. linalool 0.3 1.8 - 8. methone 2.4 6.8 0.3 8a. naphthalane 3.1 8b. Unknown aromatic cpd. - 1.3 8c. Unknown C12H16 (?) 3.1 9. methyl naphthalene 2.6 15 10. methyl N decanoate 6.8 26 13. ethyl decanoate 3.4 - 17. dodecanol 9.5 - 18. 4-ionone 21 19 1.8 20. dihydroactinidiolide 2.1 0.9 0.3 22. dodecyl acetate 7.6 - 0.5 26,27. heptadecane 35 - 0.5
Unknowns 3.0 15 2.2
Table XXI. Relative Percentage Composition of the Volatile Components of Boronia megastigma.
ii) Discussion
The relatively high proportion of monoterpene components
in the headspace from the flowers was of considerable
interest, as the aroma from the flowers was considerably
"cleaner" than that of the solvent extracted material.
Leggett [215] reported the presence of a number of
components not normally found in natural Boronia extracts
when he examined a sample of commercial Boronia absolute.
The addition of the compounds, menthol, piperitone, /3-
ionone, menthyl propionate and elemol; may be an attempt by
commercial interests to correct this difference in odour
between the extract and the flowers.
-101 -
Leggett has divided the volatile oils from Boronia
megastigma into a number of different chemotypes on the
basis of the presence, or absence, of certain components.
The headspace from the flowers provided sufficient evidence
to identify the plant as belonging to a particular class on
the basis of the presence of menthone, methyl decanoate,
ethyl decanoate, methyl naphthalene, although the
concentration was low.
A Tenax sample collection tube in conjunction with an
efficient separation and identification system, such as a
GC/MS system has been shown to be an effective method for
the collection and analysis of Boronia volatiles. The system
as outlined could, with a few modifications, be utilised to
determine rapidly the optimum time for harvesting flowers
for commercial purposes. Monitoring the relative
concentrations of the physiochemi,cally active components
over a period of time would provide valuable information for
the commercial grower as to the optimum harvest time under a
variety of weather conditions, without having to harvest
selected areas of a field. The technique should also be
applicable to other essential oil crops, as the steps of
(comminution, extraction, and evaporation would not be
required.
- 102-
CHAPTER VI
COMPOSITION CHANGES OF VOLATILE COMPONENTS
OF PINUS RADIATA.
Introduction
The volatile components of Pinus radiata have been
reported by a number of authors in the past decade generally
using one specific method of sample collection and analysis.
This chapter outlines a number of complementary techniques
that have been used to document the changes in the volatile
components occurring upon injury of a tree. Wide variations
in the composition of the major volatile monoterpenes
between individual trees made comparisons difficult. Trees
were selected that appeared to be similar in initial
volatile composition so that changes occurring could be
documented on two individual trees using the techniques
available.
Bannister [217] compared the volatile components of 189
trees of Pinus radiata in several locations in New Zealand
and California and found a wide variation in the percentage
composition. The percentage of -c-pinene varied from 12.6 to
58 percent. The total of plus/3 -pinene was of the
order of 98 percent. Other indentified components were
camphene, limonene and 4-phellandrene. Previous work by
Mirov [218] had identified many of the other major
constituents of various pines including radiata.
- 103-
Damage to Pinus radiata by the introduced Sirex noctilio
wasp prompted investigations into the volatiles of damaged
trees by Simpson and McQuilkin [219] who noted only minor
changes in composition with time after felling of the tree,
even though the attractiveness changed markedly over the
first three weeks. The authors of this paper trapped the
volatiles from sawn logs, with ends sealed, by cryogenic
traps, and noted the change in response of components by the
antenna of S. noctilio. The individual volatile components
identified were ,c -pinene, camphene,/3-pinene, sabinene,
mycrene, 3-carene, limonene ,/2-phellandrene, x-terpinene,
p-cymene, terpinolene as well as camphor, pinocamphone,
isopinocamphone and trans pinocarveol. Tentatively
identified were fenchone, terpinen-4-ol, thymol methyl
ether, borneol and citronellol.
Work done by Madden [220] showed that the timing and
duration of attack of S. noctilio correlated with the degree
of stress undergone by the host tree. Felling of a tree
induced immediate attack with susceptibility for
approximately 14 days. Girdling was correlated with attack
9 to 12 days later, but susceptibility remained for an
extended period i.e. over one season. It was thought that
debilitation of the tree and the reduction of soluble solids
caused the release of the attractant from the cambiumphloem
region. Injection of mucosecretion by the female wasp
appeared to worsen the initial stress condition and result
in attacks 1)3, more females. Stress induced changes altered
the tissue permeability and increased the rates of
- 104 -
monoterpene and water vapour loss through the bark [221].
Additional work has been undertaken in this project to
confirm this finding and to identify and quantify some of
the terpenes.
Alterations in tree chemistry of attacked and unattacked
P. radiata are also given by Hillis and move [222] who
observed changes in the composition of polyphenols in
sapwood, knotwood and heartwood. Ethylene has been reported
to be released in larger quantities and to correlate with
polyphenol production of an injured tree [223].
Sampling and Analytical Methods
The Pinus radiata trees used for the experimental work
were situated in a forest at Pittwater, Tasmania. The group
of trees selected was a closely planted (1-1.5m) trial plot
15 years old.
Mass spectral information, together with relative
retention times on two different capillary gas
chromatography columns, was used to identify most of the
components in the volatile oil and headspace gas samples.
Comparison of the information with literature values and
with authentic standards served to confirm the identity of
all but a few of the components isolated. OV101 and
Carbowax 20M were the two liquid phases used in the 50M
silica GC capillary columns. Conditions of operation are
set out in Table XXII.
- 105-
Gas Chromotography
Column Type carrier flow (ml/min) carrier gas
OV101 Scot (silica) 1.0 hydrogen
CW2OM Scot (glass) 1.5 hydrogen
Initial Temp. (deg.C) 50 50 Final Temp. (deg.C) 200 200 Temp. Prog. Rate (deg.C/min) 4 4 Injector Temp. (deg.C) 240 240 Detector Temp. (deg.C) 250 250 Inj. Vol. (microliters) 0.05 0.05 Detector FID FID
Gas Chromatography/Mass Spectrometry
GC Column OV101 (silica) Interface Temp. (deg.C) 250 Mode Electron Impact 70 Ev Scan Rate 1 second per decade Mass Range 20-350
Table XXII. GC and GC/MS Operating Conditions.
- 106-
A. The Composition of the Steam Volatile Components From the Bark Oil of P. radiata.
Earlier work by Simpson and McQuilkin [224] had
established the occurrence of fifty components in the steam
distillate of the bark oil. However, it was felt necessary
to document these components using the GC and GC/MS
facilities presently available. A section of the bark-
phloem was carefully removed from a number of trees and 500g
was broken up into small pieces and steam distilled. The
yield was 0.3 percent.
High resolution gas chromatography using the OV101 and
CW2OM silica capillary columns indicated the presence Of the
two major peaks,qt/. and pinene, and a number of smaller
component peaks.
The flame ionisation detector trace for OV101 is shown
in Figure XXXIV. The GC/MS total ion current trace for the
equivalent CW2OM trace is shown in Figure XXXV. Scan
numbers and peak identity information is shown in Table
XXIII. A number of minor components were not identified but
mass spectral information and the relative retention index
was determined for each component. Elution order of some
components did not always agree with the literature values
[212] but a slightly higher programming rate and changes in
the retention properties, (especially of the CW20M), could
account for the discrepancies.
- 107 -
Identity Composition Scan No.
Ret. Index
Base Peak
Parent Peak
a-pinene 32.8 154 1023 93 136
camphene 0.5 176 1075 93 136
B-pinene 55.2 205 1120 93 136
pinane ? , 0.1 226 1140 95 138
A3 carene 0.9 231 1145 93 136
myrcene 1.8 240 1150 93 136
cymene (type) 0.1 249 1175 119
limonene 2.4 257 1195 68 • 136
dodecane 0.1 271 1200 57 170
B phellandrene 0.4 273 1215 93 136
unknown 0.1 278 1220 71 154
m cymene <0.1 313 1265 119 134
p cymene 0.2 321 1270 119 134
a terpinolene 0.1 329 1285 121 136
C13
hydrocarbon + unknown <0.1 349 1300 57 184
myrtenol <0.1 371 1335 79 152
unknown mixt 0.1 396 1365 97 154
cymene (type) <0.1 403 1375 119 134
unknown 0.2 416 1390 67 152
bornyl acetate 0.1 430 1405 95 158
fenchone 0.1 438 1410 81 152
1450 a-dimethylstyrene 0.1 466 *1278 132 1 .32
unknown sesquiterpene <0.1 495 1485 119 204
a copaene <0.1 518 1520 161 204
dimethylstyrene plus unknown <0.1 523 1525 117 204
iso pinocamphone 0.2 549 1545 83 152
pinocamphone 0.1 575 1580 83 152
1585 linalool 0.1 579 *1506 71 154
unknown sesquiterpene <0.1 588 1595 161 204
1605 iso borneol <0.1 601 *1660 95 -
1015 fenchol 0.4 608 *1575 81 204
6 tert. butyl cresol <0.1 614 1620 149 164
terpinene-4-ol 0.1 628 . 1630 71 154
cont...
- 108-
myrtenal .+0.1 651 1660 79 150
transpinocarveol 0.8 678 1690 no spectra printed
borneal plus unknown 0.1 683 1700 95
1728 a terpineol 0.6 714 *1661 59 not present
muurolene <0.1 728 1730 105 . 204
A cadinene <0.1 755 1760 161 204
unknown 0.3 795 1810 79 152
calamenene <0.1 819 1840 159 204
p cymene-8-ol 0.1 840 1850 135 . 150
* represents literature values.
Table XXIII. Mass Spectral and Retention Index Identification Data for Whole Bark Oil Distillate P. radiata. CW2OM Capillary Col. 50-200 deg. C. 4 deg./min.
Table XIII lists over forty components in the steam
distillate of the bark oil from P. radiata. Twenty or so
other components were noted in varying trace concentrations.
Many of these were not adequately resolved on either the
OV101 or CW2OM columns, and rearrangements to isomers would
probably occur on separation. This work has substantially
confirmed the results of Simpson and McQuilkin [224].
29
2 I
4 6
- 109-
auau!d -.3
---'
.
0 c U c
1 ,r
0 C
<
—
4,
• .7
L
0 > , m U 0 C _ a o c E 4,
-
u
,
•
L 20
30
40
50 60 70 Time (mins) 80
Figure XXXIV. GC Trace Bark Oil P. radiata OV101 Capillary Col. 50-200 deg. C at 2 deg./min.
CRL:IC3S0
222 112:22
17:11
85557
7 . 7
7S
0
7E2 WM
123 24.2 20:53
27:44
vos
az. 1116 2:22
9
651
-
l v 2
Figure XXXV. TIC Trace Bark Oil P. radiata CW2OM Capillary Col. 50-200 deg. C at 4 deg./min. Peak Identification Table XXII.
- 110-
B. Collection of Headspace Samples From The Bark of P. radiata.
Collection and trapping of the volatile components
emitted from the bark were undertaken by placing alpiAythene
sheet collection bag round the tree and drawing the
headspace through a Tenax sample tube to collect the
components.
Each trap consisted of three pieces of 40mm wide
aluminium strip bent so that the upper and lower ends rested
against the trunk and the centre section stood away 100mm
thus providing an annular space to collect the volatiles.
q0 0mm
Figure XXXVI. Aluminium Framework for Headspace Trap.
The three aluminium strips were placed round the tree at
120 degree intervals and polythene film was wrapped round
the outside and held in position by rubber straps and a
bolted cover strip over one of the aluminium supports.
Large 16mm dia. bolts with 4mm centre tapped holes, held
the cover strip in position and at the same time allowed
access to the headspace inside the polythene. The centre
hole was plugged by a small threaded brass bolt before and
after sampling.
Placement of the traps round the tree was undertaken 24
hours before sampling of the headspace commended. Headspace
sampling was undertaken by attaching a 170mm long glass tube
filled with previously conditioned Tenax GC to the 16mm dia.
bolt with a suitable length of Teflon tubing. The centre
4mm bolt was removed and the glass tube butted up to the
hole through to the airspace between the ;polythene sheet and
the trunk. Air was drawn through the Tenax at a constant
flow rate by regulating a needle valve in the gas stream
before the air pump.
Prior to the placement of polythene sheet headspace
traps round the tree, a sample of headspace from the sheet
was taken by placing it in a previously cleaned large glass
vessel and trapping the components given off when the vessel
was warmed. The glass vessel was cleaned by heating to 600
deg.0 and then allowed to cool. Polythene sheeting was
placed loosely in the vessel and the volatiles adsorbed by
withdrawing air from the vessel through a Tenax trap. Dry
high purity nitrogen was admitted to the vessel via another
Tenax tube. This blank run was made in order to
characterise any components that may have resulted in using
polythene as a containing medium for plant volatile
headspace traps.
Considerable quantities of volatile material were
emitted by the polythene sheet (Figure XXXVII) and the mass
spectra and retention times for the major peaks were
recorded for future reference.
- 112-
14E16
792
7 5 1 2
468
9 3
663 73S 2
868
4'S
.7Q4
3 9
23
zsea
SOO C.S.9 CO9 C.11
13313 ze 315 27 ■ 61
Figure XXXVII. TIC Trace of Sheet Polyethylene Volatiles. OV101 Capillary Col. 50-200 deg. C at 4 deg./min.
1269 31. 9
*at £1
- 113-
C. A Comparison of Bark Volatiles From a Girdled P. radiata.
Examination of the volatiles emitted from the bark above and
below the girdle of a standing Pinus radiata were made to
document the changes that occurred when the tree was placed
under stress. Samples of the headspace and bark oil were
collected and a moisture trap was used to determine the
transpiration difference between the bark above and below
the girdled section of the trunk.
The tree selected was 15 years old and 160mm in diameter at the
girdling point. A 50mm wide ring of bark was removed from the
trunk 2m from the ground and the headspace traps were placed
round the trunk immediately above and below. A 14 day time
interval was allowed-between girdling the tree and the
sampling of the headspace as this marks . the initial stage
of attractiveness for S. noctilio.
Headspace from the trunk above and below the girdle of a Pinus
radiata tree was examined by adsorbing the volatiles on a
Tenax sample tube and GC and GC/MS techniques were used
to identify the components.
The samples were collected in early March 1981 just
before the end of a relatively dry summer period. A previously
dried and weighed copper sulphate tube placed in series with
the Tenax trap allowed the water transpiration of the two
sections of the trunk to be calculated. Air was withdrawn at a
rate of 41mL/min for two hours i.e. a total volume of 4.92L.
-114-
The volume of headspace round the trunk enclosed by the polythene
sheet was calculated to be 9.99L. The copper sulphate tube was
in series for 1 hour and therefore the volume of moist air was
2.46L in each case. Moisture adsorption above girdle was
0.0096g and below girdle was 0.0137g, or expressed in terms
of area of bark 12.5 and 21.6 mg. m -3 . h-/ . These figures are
in agreement with the findings of Madden [221] although a
slightly different technique was used to measure the rate
of water loss.
Following the removal of the headspace trapping framework from
the tree, sections of bark from above and below the girdle were
removed for distillation of the steam volatile oil. A comparison
of the composition of the two oils may provide an indication of
changes that occur in conjunction with the volatiles released
through the bark.
Traces of the GC run on the two samples of distilled bark ,
oil are shown in Figures XXXVIII and XXXIX. The runs were conducted at
relatively high sensitivity (full scale deflection representing
0.2 percent of the mixture), to highlight the differences in the
oil. Identification of a number of the peaks was not possible
due to very small quantities present and the inability to
separate sufficient quantities for confirmatory MS or infrared
spectra. Peak numbers and where possible identification
information are set out in the following table (Table XXIV).
15
Figure XXXVIII. GC Trace of Bark Oil P. radiafa Below Girdle. OV101 Capillary Col. 50-200 deg. C. at 2deg./min.
4 3 5
30
19
1,v11 A.44,,J101 V4AAJ)
2
13
12
26' 36
—115—
24
I 30 ,
13
0 35
3 ' 3
-7 II 12 29
1 I 15 22
26
PI .
14
qkrLI 1\ kA9
I 17 :ic,,9
1 , A 0
/\-\,/■"&ik\i^iv\i' ''')
. d
i\l u- I RI ;
Figure XXXIX. GC Trace of Bark Oil P. radiata Above Girdle. OV101 Capillary Col. 50-200 deg. C. at 2 deg./min.
FID
Res
p ons
e-3
1124
334
4
167
20
16
jt a 1 Da Zica 380 0.0 2.23 6141 lase
8223 868 16140 20110
1 729 Begi 2.3132 26132 33:17
421
422 13327
733739 G .F . =2
—54 8
60
S'S
4 4
2 9
--1--- 208 le:3
f ------1— ota 133e
i i ' £90 16:53
i - - 4-----r---T---T---e 600 702 202 Z023 23:St 27:13
1-- 322 32.25:
1,—. A - r
glee ems 3325
--T-- , V32 Gel7
5 s
81
671
- 116-
Figure XL. TIC Trace of Bark Oil P. radiata Below Girdle. OV101 Capillary Col. 50-200 deg. C. at 4 deg./min.
Figure XLI. TIC Trace of Bark Oil P. radiata Above Girdle. OV101 Capillary Col. 50-200 deg. C. at 4 deg./min.
- 117-
Peak Identify No.
1 tricyclene ? 2 -e-pinene 3 /3-pinene 4 pinane 5 myrcene 6 73phellandrene 7 limonene 8 ? 9 ? 10 ? 11 fenchone 12 ? 13 fenchol 14 ? 15 ? 16 ? 17 ? 18 ? 19 transpinocarveol 20 ? 21 borneol 22 ? 23 terpinene-4-ol 24 °4 terpineol 25 myrtenol 26 verbenone 27 ? 28 citronellol 29 mixture 30 ? 31 ? 32 thymol (or carvecrol) 33 ? 34 ? 35 ? 36 ? 37 ? Other
Rel.Ret. Time
0.974 1.000 1.056 1.077 1.090 1.103 1.114 1.132 1.146 1.159 1.177
Percentage Composition Below Above - Girdle Girdle
4.8 3.0
28.9 16.1
57.8 66.8
0.3 -
1.2 1.2
0.7 '<0.1
1.3 2.3
1.1 0.7
0.1 <0.1-
<0.1 -.(0.1 -<0.1
1.188 .D .4;0.1 0.1
1.219 0.2 0.2 1.325 (- 0.1 0.1 1.627 0.1 0.2 1.772 ,< 0.1 '.<0.1 1.786 cO.1 0.3 1.900
,-, <0.1 ')<0.1
1.922 0.1 0.3 1.963 <0.1 0.1 1.976 0.1 0.1 1.988 <0.1 0.1 2.031 <0.1 0.1 2.050 0.6 1.8 2.067 -4:0.1 0.1 2.081 %0.1 0.3 2.107 \0.1 0.3 2.115 %0.1 0.6 2.139 0.3 1.1 2.169 0.3 0.4 2.219 -.(0.1 0.3 2.227 0.2 1.2 2.238 -.(0.1 0.5 2.249 -40.1 <0.1 2,264 0.2 1.1 2.317 -<0.1 0.6 2.344 0.1 0.4
0.3 0.4
Table XXIV. Peak Numbers and Percentage Composition of Steam Distillate of Bark Oil Below and Above Girdle of Pinus radiata.
The bark oil below the girdle contained a larger
proportion of the more volatile components but generally,
the two oils were very similar in the oxygenated and
sesqui-terpene regions of the trace. The oil below the
-118-
girdle contained a slightly larger quantity of solvent hence
the relative difference in peak area ratios in the traces.
Quantitative interpretation of the results on the basis
of the one set of samples is suspect and further samples
would be required to confirm any differences such as the
apparent increase in relative concentrations of the
oxygenated sesqui-terpenes eluting towards the end of the
chromatogram in Figure XXXIX.
Comparison of the GC traces of Figures XXXVII and XXXIX
with the corresponding GC/MS traces (Figures XL and XLI)
reveals loss of the and /3-pinene and early monoterpene
components, and a massive increase in the relative
proportion of oc terpineol. This may be aue to the use of a
splitter in the inlet of the GC/MS unit reducing the amount
of volatile components reaching the inlet of the GC column,
or to evaporation during sample transfer operations. The
initial percentage composition figures shown in Table XXIV
represent an accurate reproduceable comparison of the bark
oils as three sampling runs showed only small variations.
Ten microliters of Freon (dichloro difluoromethane) was
injected into the headspace, prior to sampling, to act as an
internal standard. In each case the recovery of the added
solvent was within acceptable limits (90 percent for
headspace components above the girdle and, 86 percent for
headspace components below the girdle).
- 119 -
I 2847
5
8
2:ZG caa 17,2E
es, 64-- o: 12 ,r7 6:S7 10:CZ
722 OOP 522 C0.27 C7IZ C7:C7 22:SI
Figure XLII. TIC Trace Headspace P. radiata Below Girdle. OV101 Capillary Col. 50-160 deg. C. at 4 deg./min.
76
1 IGO 2443 290 CA2 COO 7aa 2:ZI Gl1C i40:0 13120 IS:SC COI12 Z2:3S EGaSC
102 Z20 222
Figure XLIII. TIC Trace Headspace P. radiata Above Girdle. OV101 Capillary Col. 50-160 deg. C. at 4 deg./min.
- 120-
The volatile headspace TIC trace for components trapped _
from the bark below and above the girdle are shown in
Figures XLII and XLIII. The traces show very few
differences in the qualitative composition of the volatiles.
Each sample was collected under identical conditions (2
hours sampling time at the same flow rate of 'dry' air), and
quantitative measurements show that the amount of volatiles
released from the bark above the girdle was greater than the
amount released from below. This result in apparent
contradiction with the composition of the oil distilled from
the bark as shown in Table XXIV. Table XXV details the
quantitative information determined from GC runs on
duplicate headspace samples and related back to the MS
traces.
H/S Below Girdle Scan No. % Comp.
H/S Above Girdle Scan No. % Comp.
198 0.1 220 0.8 307 29.4 229 27.3 317 1.0 235 2.9 352 68.0 261 58.0 nd 279 0.6
398 1.1 293 2.1 0.4 8.3
Component Identity
tricyclene ? .,c-pinene camphene /3-pinene myrcene limonene Other
Table XXV. Percentage Composition and Component Identification P.radiata Headspace Above and Below Girdle. nd - not detected
The trace components present in the headspace were
difficult to identify due to the large proportions of
and /3 -pinene. A greater number of components were present
in the headspace from above the girdle, however many were
present at a level below the detection limit of the GC/MS.
- 121-
Attack by S.noctilio occurs in greater numbers below the
girdled or injured section of a tree [220], and therefore,
the attractive component, if such a component exists may be
present at a very low concentration. Alternatively, the
presence of oxygenated components may act as a repellent to
the insect and reduce the incidence of attack above the
girdled section of the tree [225]. Headspace sampling using
porous polymer trapping techniques may not provide
sufficient capacity to trap low concentration components
(40.1%) in the presence of massive quantities of other
components.
- 122-
D. Composition Changes of Bark Headspace of P. radiata.
•
Changes in the volatile components emitted from the bark
of a number of trees were examined using a gas tight syringe
and direct injection onto a packed GC column. Wide
variations in the quantitative composition of monterpene
components of P.radiata have been reported [217], and bark
samples were collected from 7 trees of similar age and
appearance to determine the range of the two major
components.
A 50mm wide section of bark was removed from round the
circumference of each tree and placed in a glass jar fitted
with a lid containing a rubber septum. The containers were
immediately taken to the laboratory and heated to 40 deg.0
and 4mL of the headspace was injected onto a 2m CW2OM packed
GC column. The FID traces of the 7 samples recorded at an
isothermal column temperature of 60 deg.0 are presented in
Figure XLIV. Peak identities and concentrations are
recorded in Table XXVI.
After 6 and 14 days, aditional headspace samples were
taken for analysis using,the same method as outlined above.
The traces recorded on the sixth -day were similar to the
ones illustrated in Figure XLIVa however marked changes had
occured by day fourteen. Rearrangement of .C-pinene to
tricyclene had occured with many of the bark samples in the
closed glass container [226],( Figure XLV).
XI
13- er ii leo XII
1. - terpinetA
II
IX X
P - Cp1ICIIC -terpincol
OH HO
•H 2 0 H'' OW"
'OH
--- II III IV V VI
/1-pinctie rattiplultic tricyclenc terpitiolenc (lipctitenv
OH OH .
VIII -y-terpinenc
XV XVI XVII XVIII ecp 10- em lo- borneoI isobonIcol
fenclmI
nt-pincne
L r VII
a-terpincne
XIV IA-cincole
OH
- 123-
Figure XLV. Terpene Products Resulting From Hydration and Isomerisatibn ofoe-pinene [226].
b)
a)
I I :
;
1
Figure XLIV. P. radiata Bark Headspace. 4mL direct injection on CW2OM packed col. a) Day ,O. b) Day 14.
- 125 -
Tree Number Component 1 2 3 4 5 6 7
1. 01.-p1nene 42.3 36.1 24.5 26.3 34.1 23.7 31.4 2. camphene 3.4 3.8 3.3 4.9 3.9 4.1 2.9 3.4-pinene 41.3 38.0 32.5 37.9 39.4 38.6 48.5 4. myrcene 1.8 12.0 13.8 13.9 6.3 12.5 5.7 4a. unident. 0.4 2.1 1.7 5. limonene 8.0 23.4 13.4 11.6 18.6 9.2
Table XXVI. Percentage Composition of Headspace from Samples of P.radiata Bark. CW2OM Packed GC Col.
Trees 5 and 2 selected for the previously described
headspace work, and samples of the headspace were collected
from above and below the girdle by filling a Teflon gas
sample bag. Direct injection of 4mL samples of headspace
onto the packed CW2OM column confirmed the higher rate of
release of monoterpenes from the bark above the girdle
(Table XXVII).
H/S Above Girdle H/S Below Girdle Component Peak Area % Comp. Peak Area % Comp.
Unknown' 1234 4.6 1043 20.7 -c-pinene 10249 38.4 1094 21.8 camphene 632 2.4 1167 23.2 /3-pinene 14565 54.6 1721 34.2
Table XXVII. A Comparison of Peak Areas (arbitary units) and Percentage Composition of Headspace Components Collected by Gas Sample Bag from P.radiata.
The relative error for the headspace sample collected
from below the girdle would be high due to the small peak
heights (Figure XLVI), but serve as an indication of the
proportions of volatiles released.
- 126 -
CHAPTER VII
CONCLUSIONS
Techniques have been described for the sampling and
identification of trace amounts of volatile organic
compounds from natural products and air samples. Tenax has
proved to be a versatile trapping medium for the collection
of a wide range of organic compounds from gases to high
molecular weight terpenes. The equipment used to trap the
volatile components is relatively simple; consisting of a
Tenax sample collection tube, a flowmeter and an air pump;
thus enabling the collection of samples in field situations.
The quantity of material trapped can be controlled by the
volume of air passed through the trap, up to the point where
breakthrough of the most volatile component occurs. This
point is determined by conditions such as the temperature,
flow rate, and chemical nature of the component, and can be
monitored by the use of a second back-up sample tube in
series with the first.
Limitations of the sample collection procedure include
the early breakthrough of some low molecular weight gases,
and the difficulties associated with the detection of trace
quantities of components in the presence of large quantities
of material eluting at the same time. The selection of
other trapping mediums with different polarities and the use
of subambient temperature programing on a GC - would assist in
overcoming some of the above problems.
- 127-
Desorption of trapped components by heating and
secondary trapping within a U tube enables optimium
introduction of the sample onto the GC column using flash
injection techniques. To prevent thermal degradation of the
sample, elution temperatures and times need to be monitored
to ensure adequate recoveries with minimum alteration of
labile components.
The quantitation of components in complex mixtures of
volatile unknowns presents problems. The adsorption and
desorption efficiency of each component will vary according
to the concentration of other components in the mixture and
the chemical nature of the adsorbent, as well as on other
factors such as flow rate and temperature. Tenax provides a
versatile trapping medium for many complex mixtures and
quantitation may be achieved using addition techniques for
components of interest.
Identification of separated components was generally
carried out "on the fly" using GC and GC/MS techniques as
there are considerable difficulties involved in collecting
the microgram to low nanogram quantities of material
separated by the high resolution capillary GC columns, and
performing off line identification. Additional spectral
information was often required to complement the GC
retention time and mass spectral information that was
available. The introduction of a Fourier-transform infrared
system coupled to the GC will assist in the confirmation of
- 128-
the identity of many of the trace components detected in the
samples examined in this work.
- 129-
REFERENCES.
1 NOVOTNY, M., Hayes, J.M., Bruner, F., Simmonds, P.G. Science, 189, 215(1975)
2 VERSINO, B., Knoppel, H., DeGroot, M., Peil, A., Poelman, J., Schavenberg, H., Vissers, H., Geiss, F. J.Chromatogr., 122, 373(1976)
3 CONKLE, J.P., Miller, R.L., Edgewood Arsenal Spec.Publn. E0-SP-76001 (1976)
•
4 GIANNOVARIO, J.R., Grob, R.L., Rulon, P.W. J. Chromatogr., 121, 285(1976)
5 BEROSA, M., J.Gas Chromatogr., 2, 330(1964)
6 BAGGETT, M.S., Morie, G.P., Simmons, M.S., Lewis, J.S., J.Chromatogr., 97, 79(1974)
NARAIN, C., Marron, P:J., Glover, J.H. "Gas Chromatography" 1972 (S.G.Perry Ed.) "The Analysis of Gaseous Pollutants" Institute of Petroleum (U.K.) (1973)
WILLIS, D.E., Engelbrecht, R.M. J.Gas Chromatography, 5, 536(1967)
10 BAKER, R.A., Wat.Res., 4, 559(1970)
11 BAKER, R.A., Wat.Res., 3, 717(1969)
12 TYSON, B.J., Carle, G.C. Anal .Chem., 46, 610(1974)
13 TERANISHI, R., Mon, R.T., Robinson, A.B., Cary, P., Pauling, L. Anal .Chem., 44, (1),18(1972)
14 COPIER, H., Schutte, L., J.Chromatogr., 47, 464(1970)
15 De GREEF, J., De Profit, M., De Winter, F., Anal .Chem., 48, 38(1976)
16 BRUNER, F., Ciccioli, P., Di Nardo, F., J.Chromatogr., 99, 661(1974)
17 HOFFMANN, D., Patrianakos, C., Brunneman, K.D., Gori, G.B.,
Anal.Chem. 48,(1), 47(1976)
18 Di CONCIA, A.,_Samperi, A., Anal .Chem., 46, 140(1974)
- 130 -
19 ACHESON, M.A. Wat.Res., 10, 207(1976)
20 SUFFET, I.H., McGuire, M.J. Envir.Sci.Technol., 12, (10), 1138(1978)
21 GROB, K., Grob, G., J. Chromatogr., 62, 1(1971)
22 RASMUSEN, R.B. Amer.Lab., Dec. 55(1972)
23 SAUNDERS, R.A. "Analysis of Spacecraft Atmospheres"
NRL Rept.5316 (1962)
24 CHAINTELLA, A.J., Smith, W.D., Umstead, M.E., Johnson, J.E., Am.Ind.Hyg.Assn.J., 27, 186(1966)
25 HANGARTNER, M., Inter.J.Environ.Anal.Chem., 6, 161(1979)
26 BUELOW, R.W., J.Am.Wat.Wks.Ass., 65, 195(1973)
27 RUBENSTEIN,R.N., Silchenko, S.A. J.Chromatoqr., 9, 264(1962)
28 DREW, C.M., Johnson, J.H., J.Chromatogr., 9, 264(1962)
29 WIDMARK, K., Widmark, G. Acta.Chem.Scand., 16, 575(1962)
30 CARTWRIGHT, M., Heywood, A., Analyst., 91, 337(1966)
31 CROPPER, F.R., Kaminsky, S., Anal.Chem., 37,660(1965)
32 NOVAK, J., Vasak, V., Janak, J. Anal .Chem., 37, 660(1965)
33 DRAVNIEKS, A., Krotoszynski, B.K., J.Gas Chromatogr., 10, 367(1966)
34 AUE, W.A., Teli, P.M., J.Chromatoqr.Sci. 62,15(1971)
35 BELLAR, T.A., Brown, M.F., Sigsby, J.E., Anal.Chem., 35, 1925(1963)
35a BIERL. B.A., Beroza, M., Ruth, J.M., J.Gas Chromatogr., 6, 286(1968)
- 131 -
36 STRAFFORD, N., Stouts, C.R.N., Stubbings, W.V. "The Determination of Toxic Substances in Air" I.C.I., Heffer Ed., Cambridge, Eng., 1956
37 ADAMS, D.F. Health Lab.Sci., 12, (1975)
38 DIMITRIADES, B., Health Lab.Sci., 12, (1975)
39 BAUM, E.H., J.Gas Chromato2r., 1, 13(1963)
40 HOLLIS, 0.L. "Advances in Chromatography 1956". A. Zlatkis and L.S. Ettre Eds., Preston Tech. Abstracts Co., Evanston. p.56(1966)
41 HOLLIS, 0.L., Hayes, W.V. J.Gas Chromatogr., 4, 235(1966)
42 BERTSCH, W., Chang, R.C., Zlatkis, A., Chromatographia, 6, 67(1973)
43 PALFRAMAN, J.F., Walker, E.A. Analyst, 92, 71(1967)
44 ZLATKIS, A., Kaufman, H.R. J.Gas Chromatogr., 4, 240(1966)
45 ROGOSA, M., Love, L.L. Appl. Microbiol., 16, 285(1968)
46 PALFRAMAN, J.F., Walker, E.A. Analyst, 97, 535(1967)
47 BURGER, J.D., J.Gas Chromatogr., 6; 177(1968)
48 BAKER, R.N., Alenty, A.L., Zack, J.F., J.Chromatogr.Sci., 7, 312(1969)
49 WHILHITE, W.F., Hollis, 0.L. J.Gas Chromatogr., 6, 84(1968)
50 JONES, C.N. Anal.Chem., 39,1858(1967)
51 SMITH, J.R.L., Waddington, D.J. J.Chromatog., 36, 145(1968)
52 JOHNSON, J.F., Barrall, E.M. J.Chromatogr., 31,547(1967)
53 DAVE, S.B., J.Chromatoqr.Sci., 7,390(1969)
54 ZLATKIS, A., Lichenstein, H.A., Tishbee, A. Chromatographia, 6, 21(1973)
- 132 -
55 VERSINO, B., de Groot, M., Geiss, F. Chromatoqraphia, 7,(6), 302(1974)
56 PELLIZZARI, E.D., Bunch, J.E., Berkley, R.E., McRae, J. Anal.Chem., 48, 803(1976)
57 BELLAR, T.A., Lichtenberg, J.J., "The Determination of Volatile Organic Compounds in Water by Gas Chromatography" EPA-670/4-74-009 Washington D.C. (Nov.1974)
58 ZLATKIS, A., Bertsch, W., Bafus, D.A., Liebich, H.M. J.Chromatogr., 91, 379(1974)
59 SYDOR, R., Pietrzyk, D.J. Anal.Chem., 50, (13) 1842(1978)
59 ZLATKIS, A., Lichenstein, H.A., Tishbee, A., Bertch, W., Shumbo, F., Leibich, H.H. J.Chromatoqr.Sci., 11, 299(1973)
60 BUTLER, L.D., Burke, M.F., J.Chromatogr.Sci.,14, 117(1976)
61 ZLATKIS, A., Bertsch, W., Lichenstein, H.A., Tishbee, A., Shunbo, F., Leibich, H.M., Coscia, A.M., Fleischer, N. Anal.Chem., 45, 763(1973)
62 PELLIZZARI, E.D., Bunch, J.E., Carpenter, B.H., Sawicki, E. Environ.Sci.Technol., 9, (6) 552(1975)
63 PELLIZZARI, E.D., Bunch, J.E., Berkley, RE., McRae, J. Anal .Lett., 9,(1) 45(1976)
64 PELLIZZARI, E.D., Caerpenter, B.H., Bunch, J.E., Sawicki, E- Environ.Sci.Technol., 9, (6), 556(1975)
65 JUNK, G.A., Richard, J.J., Grieser, M.D., Witiak, D., Arguello, M.D., Vick, R., Svec, H.J., Fritz, J.S., Calder, G.V. J.Chromatoqr., 99,745(1974)
66 BURNHAM, A.K., Calder, G.V., Fritz, J.S., Junk, G.A., Svec, H., Willis, R., Anal.Chem., 44, 139(1972)
67 BURNHAM, A.K., J.Amer.Wat.Wks.Ass., 65, 722(1973)
- 133-
68 JUNK, G.A., Svec, H.J. "The Use of Macroreticular Resins in the Analysis of Water for Trace Organic Contaminants", 21st Ann.Conf. on Mass Spect. and Allied Topics". Paper No.P1 San Fransisco, May(1973)
69 RICHARDSON, D. Ph.D. Thesis Uni.of Tas.(in Press)
70 MORRISON, J.D., Smith, J.F., Stepan, S.F. "System for the Analysis of Organic Pollutants in Water" AWRC Tech.Paper No. 28, Canberra (1977) •
71 JUNK, G.A., Richard, J.J., Fritz, J.S., Svec, H.M. "Identification and Analysis of Organic Pollutants in Water", Keith, L.H. Ed., Ann Arbor Science Publn. Mich. USA (1976)
72 NOVOTNY, M., Lee, M.L., Bartle, K.D. Chromatoqraphia, 7, 333(1974)
73 KROTOSZYNSKI, B., Gabriel, G., O'Neil, H. J.Chromatogr.Sci., 15, 239(1977)
74 MIEURE, J.P., Dietrich, M.W. J.Chromatogr.Sci., 11, 559(1973)
75 CICCIOLI, P., Bertoni, G., Brancaleoni, E., Fratarcangeli, R., Bruner, F., J.Chromatogr., 126, 757(1976)
76 DRESSLER, M., J.Chromatoqr., 165, 167(1979)
77 CRONIN, D., Gilbert, J., J.Chromatogr., 71, 251(1972)
78 GOLDBERG, M.C.., De Long, L., Sinclair, M. Anal. Chem., 45, 89(1973)
79 GROB, K., Grob, K(Jr), Grob, G. J. Chromatoqr., 106, 299(1975)
80 KOLB, B., PospisiI, P., Jaklin, M., Boege, 0. Chromatoqr.Newslett., 7, (1),1(1979)
81 DROZD, J. Novak, J., J.Chromatogr., 152 55(1978)
82 DROZD, J. Novak, J., J.Chromatogr., 136, 37(1977)
83 NELSON, P.E., Hoff, J.E. Food Technoi., 22, 61(1968)
84 BASSETTE, R., Ozeris, S., Whitnah, C.H:, Anal .Chem., 34, 1540(1962)
- 134-
85 GASCO, L., Barrera, R., de la Cruz, F. J. Chromatogr. Sci ., _7_, 228(1969)
87 HOFF, J.E., Feit,E.D. Anal .Chem., 36, 1002(1964)
88 LOPER, G.M., Webster, J.L. J.Chromatoqr.Sci., 9, 466(1971)
89 McCARTHY, A.I., Palmer, J.K., Shaw, C.P., Anderson, E.E. J.Food Sci., 28, 379(1963)
90 ARPINO, P., Giuochon, G., Anal.Chem., 51, 683A(1979)
91 BURSEY, J.T., Smith, D., Bunch, J.E., Williams, R.N., Berkley, R.E., Pellizzari, E.D., Inter.Lab., p.11 Jan/Feb(1978)
92 GROB, K., Voellmin, J.A. J.Chromatoqr.Sci., 8, 218(1970)
93 LIPSKY, S.R., McMurray, W.J., Hernandez, M., Purcell, J.E., Billeb, K.A. J.Chromatogr.Sci., 18, 1(1980)
94 HURT, S.G., Baudean, J.E., Purcell, J.E. Chromatoqr.Newsletter, 8, 32(1980)
95 HURST, R.E., Settine, R.L., Fish, F., Roberts, E.C. Anal.Chem., 53 2175(1981)
96 CORKHILL, J.A., Giese, R.W., Anal .Chem., 53, 1667(1981)
97 CARTER, M.H., J.Chromatoqr., 235, 165(1982)
98 PARLIMENT, T.H., Spencer, M.D. J.Chromatoqr.Sci., 19, 435(1981)
99 Pittsburg Conference, Atlantic City, New Jersey March, 8-12, 1982
100 ISSENBERG, P., Hornstein, I. "Advances in Chromatography", J.C. Giddings, R.A. Keller Eds., Marcel Dekker Inc., N.Y., Vol.9, 304(1970)
- 135 -
101 MERRITT, C., Walch, J.T. Anal.Chem., la, 110(1963)
102 BLASS, W., Riegner, K., Hulpe, H., J.Chromatogr., 172, 67(1979)
103 NOVOTONY, M., Lee, M.L. Experimentia, 29, 1038(1973)
104 ADLARD, E.R., Creaser, L.F., Mathews, P.H., Anal .Chem, 44, 64(1972)
105 BARTLE, K.D., Lee, M.L., Novotny, M., Int.J.Envon,Anal.Chem., 3, 349(1974)
106 NOVOTNY, M., Lee, M.L., Low, C.E., Raymond, A. Anal.Chem., 48, 24(1976)
107 ETTRE, L.S., Purcell, J.E., Norem, S.D., J. Gas Chromatogr., 3, 181(1965)
108 ETTRE, L.S., Purcell, J.E., Billeb, K., J. Chromatogr., 24, 335(1966)
109 BRENT, D., Rouse, D., Varian- Mat., CH5-DF/MAT 311 Appin.Note No.12
110 LEVSEN, K., Wifp, H.K., McLafferty, F.W. Org.Mas Spectrom., 8, 117(1974)
111 SMITH, D.H., Djerassi, C., Maeur, K.H., Rapp, U. J.Am.Chem.Soc., 96, 3482(1974)
112 BEYNON, J.H., Cooks, R.G., Amy, J.W., Baitinger, W.E., Ridley, T.Y., Anal .Chem., 45, 1023A(1973)
113 KONDRAT, R.W., Cooks, R.G. Anal .Chem., 50,(1), 81A(1978)
114 MAJORS, R.E. J.Chromatogr.Sci., 15, 334(1977)
115 MAJORS, R.E. Amer.Lab., 7, 13(1975)
116 KUCERA, P., Manius, G. J.Chromatogr., 219, 1(1981)
117 KRSTULOVIC, A.M., Rosic, D.M., Brown, P.R. Anal .Chem., 48, 1383(1976)
118 SCHUETZLE, D., Riley, T.L., Prater, T.J., Harvey, T.M., Hunt, D.F. Anal .Chem., 54, 265(1982)
- 136-
119 MOORE, J.C. J.Polym.Sci., Part A2, 835(1964)
120 KRISHEN, A. J.Chromatogr.Sci., 15, 434(1977)
121 HENDRICKSON, J.G. Anal .Chem., 40, 49(1968)
122 TANIMURA, T., Pisano, J.J., Ito, Y., Bowman, R. Science, 169, 54(1970)
123 NOVOTNY, M., Lee, M., Bartle, K.J. J.Chromatogr.Sci., 12, 606(1974)
124 HOFFMANN, D., Wynder, D. Anal .Chem., 32, 295(1960)
125 NATUSCH, D., Tomkins, B. Anal.Chem., 50, 1429(1978)
126 COLGROVE, S.G., Svec, H.J., Anal.Chem., 53, 1737(1981)
127 KONTES SCIENTIFIC Anal.Chem., 54, 232A(1982)
128 PERRY, J.A., Haag, K.W., Glunz, L.J. J.Chromatogr.Sci., 11, 447(1973)
129 JUPILLE, T.H., Perry, J.A. J.Chromatogr.Sci., 13, 163(1975)
133 AYLING, G.M., "Spectroscopic Methods of Identification" Marcel Dekker N.Y.1974
134 CRAM, S.P., Risby, T.H., Anal.Chem., 50, 213R(1978)
135 SANDALLS, F.J., Penkett, S.A. Atmos.Environ., 11,(2), 197(1977)
136 BACHE, C.A., Lisk, D.J., Anal.Chem., 39, 786(1976)
137 McLEAN, W.R., Stanton, D.L., Penketh, G.E. Analyst, 98, 432(1973)
138 DALEN van, J.P., Coulander, R., de Lezenne, P., de Galen, L.,
Anal.Chim.Acta, 94, 1(1977)
139 QUIMBY, B.D., Delaney, M.F., Uden, P.C .., Barnes, R.M. Anal .Chem., 51, (7), 875(1979)
- 137-
140 BLUM, W., Richter, W.J., Finnigan Spectra, 11, (1974)
141 SCHOMBERG, G., Henneberg, D. Chromatographia, 1, 23(1968)
142 VOELLMIN, J.A. Chromatographia, 3, 238(1970)
143 GROB, K., Grob, G. Neue Zurcher Zeitung, Beilage "Forschung und Techntk", 7-8(1972)
144 KARASEK, F.W. Ind.Res.Dev., 113, April(1978)
145 OSWALD, E.O., Albro, P.W., McKinney,J.D. J.Chromatogr., 2B, 363(1974)
146 SWEELEY, C.C., Young, N.D., Holland, F.J., Gates, S.C. J.Chromatogr., 99, 507(1974)
147 KIMBLE, B.L., McPerron, R.V., Olsen, R.W., Walls, F.C., Burlingame ; A.L. Adv.Mass Spectrom., 7, 873(1978)
148 LIEBICH, H.M., Al-Babbili, O. J.Chromatogr., 112, 539(1975)
149 SCHUETZLE, D., Rasmussen, R.A. J.Air Pollut.Control Assoc., 28, (3), 236(1978)
150 FENSELAU, C., Anal. Chem.,49, 563A(1977)
151 BILLER, J.E., Biemann, K., Anal .Let., 7 515(1974)
152 SUMMONS, R.E., Pereira, W.E., Reynolds, W.E., Rindfleich, T.C., Duffield, A.M. Anal.Chem., 46,(4), 582(1974)
153 DROMEY, R.G., Stefik, J.M., Rindfleisch, T.C., Duffield, A.M., Anal. Chem., 48, 1368(1976)
154 SWEELEY, C.C., Gates, S.C., Thompson, R.H., Hasten, J. "Quantitative Mass Spectrometry in Life Sciences" A.P. de Leenheer, R.R. Roncucci, Eds.; Elsevier Publ. Co., Amsterdam (1977)
155 GATES, S.C., Smisko M.J., Ashendel, C.L., Young, N. Holland, WE., Sweeley, C.C. Anal. Chem., 50, 433(1978)
156 GROB, K., Grob, G. Chromatographia, 10, 181(1977)
- 138-
157 AXELSON, M., J.of Steroid Biochem., 8 693(1971)
158 BURLINGAME, A.L., Kimble, B.J., Derrick, P.L., Anal.Chem., 48, 368R(1976)
159 SMITH, B.T., Gillespie, R.E. Anal.Instrum., 15, 91(1977)
160 PITTS, J.N., Finlayson-Pitts, B.J., Winer, A.M. Environ.Sci.Technol., 11,(6) 568(1977)
161 TUAZON, E.C., Graham, R.A., Winer,A.M., Easton, R.R., Pitts, J.N., Hanst, P.L. Atmos.Environ. 12, 865(1978)
162 JACOBS, H.W., Syrjala, R.H. J.Am.Ind.Hyg.Assoc. 39,(2),161(1978)
163 BAUMGARDNER, R., Edgewood Arsenal Spec.Publn. EO-SP-76001(1976)
164 MURRAY, E.R. Opt.Enq., 16,(3), 284(1977)
165 KANSTAD, S.O., Bjerkestrand, A., Lund, T. J.Phys.E., 12,(10),998(1977)
166 DELANEY, M.F., Uden, P.C., Anal.Chem., 51, 1242(1979)
167 GALLAHER, K.L., Gasselli, J.G., Appl. Spectrosc., 31, 456(1977)
168 SYDOW, E. von, Anjav, K., Karlson, G. "Archives of Mass Spectral Data Nr.279" Goteberg, Sweden. Vol .1(1970)
169 ADAMS, R.P., Granat, M., Hogge, L.R., Rudloff, E.von., J.Chromatoqr., 17, 75(1979)
170 FOX, D.L., Jeffries, H.E., Anal. Chem. 53, 1R(1980)
171 BURLINGAME, A.L., Baillie, T.A., Derrick, P.J., Chizhov, 0.S., Anal .Chem., 52, 214R(1980)
172 CRAM, S.P., Risby, T.H., Field, L.R., Yu, W.L., Anal .Chem., 52, 324R(1980)
173 GILBERT, J.M., Oro, J. J. Chromatoqr. Sci., 8, 295(1970)
- 139-
174 ORO, J., Gilbert, J.M., Updegrove, W., McReynolds, J., Ibanez, J., Gil-Av, E., Flory, D., Zlatkis, A. J.Chromatogr.Sci., 8, 297(1970)
175 MURPHY, R.C., Preti, G., Nafissi, V., Biemann, K. Science, 167, 755(1970)
176 CALI, J.P., Reed, W.P., N.B.S., Spec.Publn., 422, p.21, G.P.O. Washington DC (1976)
177 LEWIS, R.G. "Accuracy in Trace Analysis: Sampling, Sample Handling, Analysis", N.B.S. Spec.Publn. 422, p9 G.P.O. Washington, D.C. (1976)
179 GUNTHER, F.A., Blinn, R.C., Kolbezen, M.J., Barkley, J.H., Harris, W.D., Simon, H.S. Anal .Chem., 23, 1835(1951)
180 SUN, T., Cohen, A., Hertz, H., Schaffer, R. 173rd National Meeting ACS., New Orleans, La. 1977
181 De RITTER, E., Cerial Foods World, 20, 34(1975)
182 CALI, J.P., Anal .Chem., 51,802A(1977)
185 RAYMOND, A., Guiochon, G. J.Chromatogr.Sci., 13, 173(1975)
186 NELSON, G.O., Harder, C.A. Am.Ind.Hyq.Assoc.J., 35, 391(1974)
187 GRUBNER, O., Burgess, W.A. Environ.Sci.Technol., 15, 1347(1981)
188 JANAK, J., Ruzickova, J., Novak, J. J.Chromatogr., 99,689(1974)
189 HOUGHTON, E. J.Chromatogr., 90, 57(1974)
190 MURRAY, K.E., Shipton, J., Whitfield, F.B. Aust.J.Chem., 25, 1921(1972)
192 BERTSCH, W., Chang, R.C., Zlatkis, A., J.Chromatogr.Sci., 12, 175(1974)
193 HELLA, S.R. and Milne, G.W.A. (Eds.) EPA/NIH Mass Spectral Data Base (1978)
- 140-
193 MARTIN, C.L., Lackey, W.W., Conkle, J.P. USAF School of Aerospace Medicine Rept. SAM-TR-77-28. Dec.(1977)
194 "Toxic and Hazardous Industrial Chemicals Safety Manual", Publ.Inter.Tech.Inf.Inst., Tokyo, Japan, 1977
195 LANGUERE, C., Aubry, M. J.Chromatoor., 101, 347(1974)
196 HODGKISS„ W.S., Johns, R.H., Swinehart, J.S. "Environmental Testing of Contaminant Producing Materials from the Integrated Life Support System" Atlantic Research Corporation, NASA Contract No.794 June 1967
197 PENFOLD, A.R., Morrison, F.R. Mus.Applied Arts and Sci. Bull.No.2, 3(1951)
198 HELLYER, R.O., McKern, H.H.G. Aust.J.Chem., 16, 515(1963)
199 LASSAK, E.V., Pinhey, J.T. Aust.J.Chem., 22, 2175(1969)
200 LODER, J.W., Moorehouse, A., Russell, G.B. Aust.J.Chem., 22, 1531(1969)
201 WILLIS, McKern, H.H.G., Hellyer, R.O. J.Proc.Roy.Soc.N.S.W,, 95, 59(1963)
202 McKERN, H.H.G. Aust.Nat.History, 352 Sept.(1967)
203 McKERN, H.H.G. J.Proc.Roy.Soc.N.S.W., 98, 1(1965)
204 GRUNDON, M.F., Senior Reporter, "The Alkaloids" - Royal Soc.of Chem., London, U.K.,_Vols.1-11.
205 HANSON, J.R., Senior Reporter "Terpenoids:and - Steroids" - Roy.Soc.of Chem. London, U.K.,.Vols.1-10
206 BICK, I.R.C., Bowie, J.H., Douglas, G.K., Aust.J.Chem., 20, 1403(1967)
207 AYLING, G.M., M.Sc. Thesis Uni.of Tas., "Terpene Composition of Essential Oils", Chemistry Dept., Uni. Tas. (1976)
208 CURTIS, W.M., "The Students Flora of Tasmania", Tas. Govt. Printer, (1967)
- 141 -
209 STEVENS, J.D. "Investigation of the Oil of Drimys lanceolata" Hons. Thesis Uni. of Tas. (1955)
210 LODER, J.W. Aust.J.Chem., 15, 389(1962)
211 CORBETT, R.E., Grant, P.K., J.Sci.Food Acric., 9, 733(1958)
212 JENNINGS, W., Shibamoto, T. "Qualitative Analysis of Flavour and Fragrance Volatiles by Glass Capillary Gas Chromatography" Academic Press, New York (1980)
213 KUGLER, E., Langlais, R., Halang, W., Hufschmidt, M., Chromatographia, 8, 468(1975)
214 YABUMOTO, K., Jennings, W.G., Yamagucyhi, M. Anal.Biochem., 78, 244(1977)
215 LEGGETT, G.W., Menary, R.C. "Boronia Production - Its Growth and Oil Characteristics", Paper pres. 8th Int.Cong.of Ess.Oils, Cannes (1980)
216 PENFOLD, A.R. J.Roy.Soc.W.A., 14. 1(1927)
217 BANNISTER, H.M., Williams, A.L., N.Z. J.Sci., 5, 4, 486(1962)
218 MIROV, N.T. Tech.Bull. U.S. Dept.of Agric.No. 1239 p1-158(1961)
219 SIMPSON, R.F., McQuilkin, R.M. Ent.Exp.& Appl., 19, 205(1976)
220 MADDEN, J.L. Bull.Ent.Res., 60, 465(1971)
221 MADDEN, J.L. Bull.Ent.Res., 67. 405(1977)
223 SHAN, L., Hillis, W.E. Phytopathology, 62, 1407(1972)
- 142-
224 SIMPSON, R.F., McQuilkin, R.M. Phytochemistry, 15, 328(1976)
225 NEUMANN, F.G., Minko, G. Aust.For,-44, 46(1981)
226 KERANEN, R. Paperi ja Puu - Papper och Ira. 3, 165(1978)
- 143 -
APPENDIX
SECTION A. Paper Published During The Course of This Work.
' SECTION B. Equipment Details. Gas Chromatography Equipment. Gas Chromatography/Mass Spectrometry
Equipment Used During The Course of This Work.
SECTION C. Mass Spectral Information From GC/MS Runs (Arranged According to Chapter)
Chapter IV Tenax Trap Volatiles.
Chapter V Drimys lanceolata Prostanthera lasianthos Bronia megastigma
Chapter VI Pinus radiata
- 144-
- 145 -
Paper in attached pocket - inside rear cover.
- 146-
GAS CHROMATOGRAPHY
• Packed column gas chromatography was performed on
a Varian 3700 gas chromatograph equiped with flame ionisation
detectors, and a temperature programme controlled oven. Two
meter long by 4mm internal diameter glass columns were used
with nitrogen carrier gas at a flow rate of 35mL per minute. •
The same GC was used for capillary column gas chromatography
using a SGE capillary column conversion kit to optimise gas flow.
GAS CHROMATOGRAPHY/MASS SPECTROMETRY
A Pye Unicam Series 204 gas chromatograph was coupled to
a VG Micromass 7070F mass spectrometer via a VG jet separator
(for packed column operation), and operated at a vacuurn of
4*10-4 Torr. Capillary columns were coupled directly to the ion
source. The system was operated at 70 EV and data was stored
and processed on a VG 2235 system coupled to a PDP 8/A626
minicomputer. The electron impact (ei) mode was used on all
GC/MS runs. Calibration of the system was performed by
injection of fluorinated kerosene mixtures. The carrier
used was either hydrogen or helium at a flow rate of
1 -1.5mL per minute.
)00 CADOOS 24 TENFIx TRAP VOLS CFR. : ICSOS
4:4
9056
GS
• 1 - gam 1
2S—JUN-81 220
• II 1
acetone
022s3
147 -
COMPONENT MASS SPECTRA
CADOOS 20 TENAX TRAP vOLS 2S—JUN-81 [Pa.: cSoo Hydrocarbon (pentadiene)
I CO
200
CROOOS 28 TENAX TRAP vOLS 2S—JUN-31 CR.:IC:SOO methylene chloride + acetone + unknown
43 25217
_
- CD
100 CANS 29 TENRx TRAP vOLS
Icsoo methylene chloride 4'1
200
;!ro :fito
CSilS
300
2S—JUN-21
; a.
a.
- 148 -
CROOOS 32 TENAX TRAP VOLS ca.:1MM Freon
2S-Jur\I-81
39112
IS
100 209
320
CFIDOOS SO TENAX TRAP VOLS
2S-JUN-8I CIA.: 1(W2
carbon dioxide
300
CADOOS 70 TENAX TRAP VOLS 2S-JUN-n-pentane + methyl pentane CFtl. : 1 CS 90
13972
300
2S-JUN-8 log zoo
CADOOS 75 TENnX TRAP VOLS ca.: csaa chloroform
GS2-7S
7— "7"-*- 2.0
benzene 25-JUN-81 CADOOS 114 TEJA 1Rcp VOLS
C: lases
13152
79
- 149 -
ee 200 S'01,7
CADOOS 119 TENAX TRAP VOLS C.RL : 1 Cat/ chloroform
'2S-JUN-81
31 3S
0
-
47
- -r r -ZOO 13211 ef.,1
CADS 245 TENRX TRAP VOLS 25-JUN-21 CAL:ICSE2 toluene
)00 CF1000S 302 T ENAX TRAP VOLS CRL:ICSSO
r ZOO
tetrachl oroethyl ene 300
25-JUN-81
1472
1. 1 1 ii
I 4 • 1 I II
- Lr
44 1Nfr;
•44
5,G38
phenol 2S-JUN--81 CROOOS 432 TENAX TRAP VOLS .
cm.:Icsso 94
3220
phenol 2S-JUN-81
lea CR0005 438 TENAX TRAP VOLS ca.: 1C:560
r 300
i 77 i
I I l i 1 , l it) , lilii, , III, 1, • III
I VA!
- 150 -
a
r-- -f Z00 2vo
25-Jurl-e leo
CRDOOS 469 TENAX TRAP V OL.S CAL:ICS:00
cresol
a
CADOOS 459 TENAX TRAP VOLS CR1. : CS0.0
128
25-JUN--B cresol
1 ;-? G
3294
3058
- 151 -
CADS 490 TENAY TRFP voLS ethyl phenol (?)
,
77 i! I !I
11
I
C I 4..1(111
fa S
CAL: 3 cses
CHDOOS ciSS TENFix vOLS GL: IM2.0
•
IF NH •
dimethyl phenol (?)
1:02
2S-JUN--8 2
I 07
1 i, .!: r • - 1,' , ... • !;', ,..,. ,i ......,,,,,.r,L, - . ,,,,.,..L.. !•,' ,...,..._.....„... , . . . r - r • . . i....-- ,
CADOOS 502 TENAx" cRL:Icsea 2 ethyl phenol (?)
2S----JUN---
.4853
I ; 1; I • ; ■ ;,t • r
;co Pi2I
CADOOS 61 TENt,Cx cRL:3csen pentadecane
7115
• ; '• I
■
t
9552
, 1 Ci
6f3
-
- 152 -
CADS 642 TENFIX TRW VOLS
2S—JUN--81 CRL:V=S22
Unknown I 4528
i 1 ; . ■ 1
■
4::111• . 1 [ ,1„...,L41 ' -1.---i ,' : u..... :,......,__, 4. - ,...._ T ri_ ...._,............_.„.
CFIDEJOS 29 FicRoLEIN + PENTAD I ENE ISOMER cm: 1C9Ø
2S-JU-9 I
C2
1 S3
667
b1/4 /!ii 13"1.1 I Pi i 1
a ea
200
RUN 2 100
127 OR I mYS L. CW20M SILICA 80-200 4
4084
41
0E0001 cAL:ID400
MYRCENE
300
26—AUG-82 4,0
4.1 947
J6 11—■ it.<1 r 108
1 '300
- 156 -
0E0001 96 ORIMYS L. CW20M SILICA 80-200 4 RUN 2 CAL:1D402 STA:E.
SOLVENT (CHLOROFORM) 26—RUG-82
3:1
100 200
0E0001 96 ORIMYS L. CI-120M SILICA 80-200 4 RUN 2 CAL:1G402 STR:E.
300
26—AUG-82 3:5
7 487
I ,
100
200
300
DE0001 116 DRIMYS L. CW20M SILICA 80-200 4 RUN 2 cRL:ID488 STA:E.
//3 -PINENE
26—RUG-82 3.39
00E: J 1 .1 .1 4,
ii •1 f 1,1
5604
E>Et, Z r4nH
on eaz V 00Z -OS U3I1IS WOZN3
00 F.• •'" . . y
I
• ! I :4r; : t
SAW I80 Bb L000 elet.at:3iTI '3:Y1S
ler
LtZ
L.L
31031\113 8'I
r
3N3bIONV-113Hd- '3:91S 004,01:11J3
3.8-9118-9?
z Nnu 00Z-08 E3I1IS 4OD13 *1 SAW 180 3t't T00030
013£
001
FS
ZS 1Z
sz:t. Z8-911W-9Z
00£
3N3NOWI1 •3:EILS 01340 :"Ii,j3 Nnu t. 00Z-08 4:13I1IS L.403r13 - 1 SAWILIO It, t00030
oez eel
199Z
3NRIONV113Hd - •3:91S 01340 I ClE30 ?8-snu-9Z z Nnu 00Z-08 U3I1 1,402:t13 1 sAwistio 0E1 100030
61
cro
- LSI -
CAL:18400 MONOTERPENE ( ?)
P CYMENE
100 200
0E0001 170 DRImYS L. CW20M SILICA 80-200 4 RUN 2 CAL:18460
^-1 P• l.r. ,11!
182 200 300
6:25 CAL:18408 UNKNOWN
-158-
619
300
26—AUG-82 S:21
0E0001 206 ORImYS L. CW20M SILICA 60-200 4 RUN 2 26-AUG -82
2
I -
leo Zee 0E0201 224 ORIMYS L. CW20m SILICA 80-200 4 RUN 2 CAL:10400 STA:E.
I SOMER OF X
S7
S
2706
100 ?.00 260
DE0001 1S8 ORIMYS L. Cw20m SILICA 80-200 4 RUN
300
26—FiUG-82 7:3
2824
26—RUG-82 4:se
2827
•
)oo zoo DE0001 279 OR 1 MYS c42em SI LI CA 80-200 4 RUN 2 CAL:16460 STA:E.
Ips . 1p
h , h
JLI 11Iiu4 e._46._ 4_ 160
-CUB ENE
.3kto 26—ALIG-82
8:46
811
! 11 I-- r —r r— r'
200 • 306 _
DEC3001 288 DRItlYS L. CAL:16400 STA:E.
CV
2
1 1
1
- 159 -
CL-42{irl SILICA 80-20 4 RUN 2
ISOMER OF X 26—AU0-22
8:2S
879
26—AUG -82 933
DE0001 304 ORIMYS L. CW20M SILICA 80-200 4 RUN 2 caL:Ipaela STA:E UNKNOWN
207
i
• 7
, • { i 1 .--' i S;S
II
: i t l ,l 1 1H I 1 i
6, WI 14 11 1.1 '
11 ill ,
1, plii 101,...T.4..14; :!1;11,,tol i ,j, )1% .1 00 ! k 444 j r.,,,,,,,,_ , 1 [1 t.,1 , , I r‘. •-,--- ...
DF0001 32S DR' MYS CAL1D'r00 Sla:E.
E0
leo 2.02 L 0-12C3ri SILICA 80-200 4 RUN 2
-BOURBONENE
300
26—ALIG—P2. 1o:13
134
1 6 1 :
. , . , , ,
. , , il I . 1•1 1 1
...t0 L ,p1114.111A011 !:0 EL ill , !ii '
go' .
! Irl
los
i ' 219
. I ! I
r :AN:3
111 „MI
100 . 200 DFOC:_101 31-2 idRIMYS L. CA-120r: Si Li CA 80-20(?; 4 RUN 2
UNKNOWN ( X + CH2 ) _ • --- CAL: 1D400
3co 26—RUG-82
10:4S
2349
- 160 -
DEEIOH1 332 Mims IJ. e',..i22t1 SILICA 60-202 4 RUN 2 0: CAL: 1040.0 STA:E.
UNKNOWN 126
_ 112
I
... , -... ; , ss
L - 1 : e3
■•._; - 1 1 11 ! 1 : I 1
1 1 11 1 1 11H1 1 :11 . 1 ilk, 111 '1 :I . 1111, 11 1
-T" i 01 1 11,114)1411141,11LrLa. 1 1,1i 4111.4 1111 ,. ,.....1.....—
2391
i•,
Y, • r •-•-; r---- 100
DEOC-M1 3S3 DRIMYS L. Cw2gr. SILICA 80-2.00 4 RUN • 2 .
CAL: 1D4 STA:E. L I NALOOL
•
41
I
• ';
' ..,1M j, I 0E0001 386 DRIriYS L. Cw2fari SILICA 80-200 CAL:1E1400 STA:E.
ZOO 300 4 RUN 2 2 .6 —AUG 2
128 CAR VU PHY LL EN E
493
I
'.. 1 .1 f l li I 1 1 1 1 1 i [1,1 1 I. 1, 1 ; .!: • i 11i 1,
I j I 11.1 , , I-0, Ilk. - It..i 11 : 1. ,.. ,.. , 1 --,..r it.:...J.1.::....:,. ..1:,..1:__Pir:!._,!...: .......,..., r !!!•. : ili .._41.1., . . •• ,..., _,..a.:,, ., 1: r- r - r,..-....--ri, :
DE.0001 4S5 CR NYS L C:-/20r1 1L. CA S0,-20 4 RUN 2 CAL: 1D400 STA:E. MONOTERPENE ALCOHOL
- 161 -
DE001:11 fiR1 NYS L CW2Pfl Li CR 8C1---2v 4 RUN CAL: 1.0400 Sin:E. •
TERPINENE-4-01
12.25
756
• I
i
i . .
. :11
,
u I 41,,,.. 1 1, ,i i,,, 4 1,1„alyj ,I. ) L_,,, 4o.. ,,I 10-is cpp
DE000] 42S P,R mYS L. C1-12Cir1 :1;11.. 1. CP. RUN 2 CAL: 111460 STA:E. SESQUITERPENE
-r------r J"----- - --r - ---- 26--FIUG-82
1 .3:40 -
1135
2 1
1r..-' .• I
1 i i
. 4 i
ll
,IOV . . -......... 'VA'.
1 , 1
400
10V1
DE000) 47G DR MYS L. CU2LI S I CR EA - 2-.;f1 4 RUN 2 CAL: 113400 STH:E• -TERPINEOL
14:S7
441
•
, . „
,. i • • • , 1 .
, .
■ .1.
I, J , _II 1 I:1 AL, i 4 :.,.. _ -r 1 r r-- -- r r ----r
lb sd
00£ 002 001 •
0 1
, •.•
3N3&1311110S3S ; '14 : ; IL; I .; '4, ,t21•.:. 1 • "1 7 .■ ,41
tr, ,..(11 :•16:1
(1:•.11.:)0 21.3.0 '• 1
00E 002 001 • :Of t i l l • 1, Pit "I
1
LS8
• 1 1
25.9 ?a-mu-9z
00E
6 00b01:1U0 '3:1215
Z Nnu 002-08 U311IS L4?M 1 SAwI80 LES 100030 002 001
'
314310 t?'I VNIOVO
681 lb
18 CV
eq
UP
b61 501
6 1
E£51
b02
El 9 l 8-9 nu- z
l9l
( ) 3N3NICIV3 • 3 :1:11S 00 1:431 -1E30 z Nna 1, 00Z-08 EMI1IS w0Zr13 *1 SAL-J180 915 100030
3NO1I213dId 81, :Si • 3 :YIS 00 b01 C1E13
Z8-9nu-SZ . z NnH i, gez-es 03I1IS Weqt13 '1 SAt-HUO EfaS 100 00 :
......—.1....._.....-- i.........- ..... .1 ,::::1 -.....J .....zt.1—.....-,-.. 1 _T I
. . Rh... „. ,. l'11-11-171-11171-j-, i.
1
9902.
- Z9T -
I
LS
1E1,
ea 001 00E t
H
rc
CB G9
11EZ
Z8-911W-9Z eaE
9b1,
(3c1A1) 1009113 1AHEW.3
00t,01: -1U3
N z al t. 00Z-08 Em 113 irs WOZ SA14 :IELLOs BEL 100030 001
4,0Z
00Z ' • 1, ' re 1 )Yi )
191
1
ssre2 Z8-91-11J-9Z
NMON4N11 '3:U1S 00 .1,01: -W3
z Nn ' e0Z-08 E1311IS 142M3 - 1 SAI4180 999 100030
00E
•
0:Gi
Z8-911E1-9Z 00E 00Z 001
09E1
bSI
II "ir" -or
I ' 116'1 II I" ' T
rb
69
10S3NM '3:111S 001,01:1H3
z Nna ta0Z-08 WDI11S 1•10ZMO *1 SAW 1E10 509 100030
S1 , 81 3NINVWV1V3 '3:U1S
Nnu eoz-os U311IS - 1 SAW 180 18S 100030
— E91 —
- 164 -
DE0001 738 DRImYS L. 0,420m SILICA 80-200 4 RUN 2 CRL:10408 STA:E. METH.. EUGENOL (TYPE)
26-AUG-82 23:11
431
57
5, 71
9 1 147
163
t 14111 py, 1111 1, 1 k 1 11! 1 1 ii11 1 11 Pi Ic 1 4 ) I I
100 '200 DE0001 771 DRImYS L. CL42011 SILICA 80-200 4 RUN 2 CAL:10400 STA:E. SESQUITERPENE ALCOHOL
300
26-AUG-82 24:13
591
41
57
204
9
161
27
5,
. 41,41(11
81
1,1,1 7.1
J1 1111 11 100 200 • 300
0E0001 779 DRIMYS L. C1420M SILICA 80-200 4 RUN 2 CRL:10408 STA:E. SESQUITERPENE ALCOHOL
26-AUG-82 24:28
603
105
100 200 DE0001 801 DRImYS L. C1-J20m SILICA 80-200 4 RUN 2 CAL: 10400 STA: E• GUAIOL
300 26-AUG-82
25:10
161
4095
4
4
57
1 3
161
1 7 9 204
11[
121 1 7 189.
41
204
1,
8
7
208 380
DE0001 826 ORImYS L. .CW2OM SILICA 80-200 4 RUN 2 mu1l-3400 STR:C. OXYGENATED SESQUITERP.
26-AUG-82 2S:S7
— 165—
01 k
619
3
GB 91
105
SS 27 133
LA)116 114 11i,I,Ay4 1. ,... 1,4,141! L 114,ji IA, I ,(1 100 200
ORImYS L. Cw20m SILICA 80-200 4 RUN 2 STA:E. MGENOL
205 153
1 46
1 97 20
0E0801 88 CAL: 13402
, 300
26-AUG-82 2G:S7
1900
•
.4
143
77 31
131
108
200 300
.s;
DE0001 861 CRImYS L. Cw2OM SILICA 80-200 4 RUN 2 CAL: 1[3.4043 STA:E. ISOMERIC GUAIOL (?)
26-AUG-82 27:3
I 9 204 GSG
-
133
41 0 105
Lii i .1 iIi 1 11
1-9
,k,. , .,.1.„ . , L. , 20
DE0001 874 ORImYS L. CI-12@M SILICA 80-200 4 RUN 2
26-AUG-82 CAL: 113400 STA:E. UNKNOWN 27:27
2
121
1-1
225
71 9) S7
204 09
311
, Ji i 1 I 11 111 1/1 1; 111 1J id il ilt itilli II Jil Ilh LIJI IL ■ 111 Tilt , ILJ b I. 1 .. 1 100 200 00
DE0331 909 DRIMYS L. C1-120m SILICA 80-200 4 RUN 2 CFit_: 113400 STA:E. UNKNOWN
26—AUG-82 2026
121
161
IS 193 1 7 4 09
fr( iJb 41,11 4 100
204
300 ti. .
200
- 166 -
0E0031 885 DRImYS L. C1420M SILICA 80-2ils 4 RUN 2 CAL: 10400 STR : E. METHYL EUGENOL + CH2 !GI
26—F1UG-82 27,48
q 71 172
3 1 1 9
7 10S
91 GE 1'1 3
I S9
d1,1 ki 1, Ili 1 11 I WI
ii
ill 1 idli
1
I, 11 11 II
9
,1,
62 202
ti 111,, 111011,11 I 1 11 11 i A , A I IA 300
26—FIUG-82 283S
ro
to 7
I 0 0 0 61. •••• • fk
100 200
0E0001 910 DRImYS L. CW20m SILICA 80-200 4 RUN 2 MIL:10400 STA:E.
0,q UNKNOWN
4J
17
m-
w
CD
71
S7
Le, ii
27
10E03
4
41 28
7 1
200 • 300 188
- 167 -
26—RUG-82 29:11
• DE0001 929 DRImYS L. CW20m SI L I CR 89-200 4 RUN 2 CAL:11)408 STA:E. MYRISTICINE (?)
192
91
6 13 1SS
1 Alps 41 11 , ktbe1l4 . 11 111 lc )4..1.4 .. I els , , r.
100 288 DE0001 101S DR I mYS L. CW20m SILICA 80-209 4 RUN 2 CAL: 1D400 STA:E. UNKNOWN
1623
1300 26—AUG-82
31:63
IC
2184
03—DEC—PW 10:c
302 - 03—DEC-80
le.ss
200
DEBRO4
/ "t
41
- 168 -
MASS SPECTRA
574 .90RONIF: FLOWER VCIL.RT
MENTHONE Peak 8)
1:43 1 /1
1$4
1.1 0 1, 1 ' Igo
BORONIR FLOWER VOLF1TILES
NAPHTHALENE (Peak 8a)
e 1
1 11
Iclat
DEf3R04 600 CRL : 1C302
19S3
03—DEC-80 Unknown Aromatic cpd (Peak 8b) 19.2
651
I,
2 Oil
;OH
03—DEC--;22. Unknown compound 19:Z7
Zoo
d fri, ■
44
I. 1 6,'. g...H ._,.,. L „,ij
I , , .!1,
i . . . .1,
23S1-
102
132
300
DEFiR04 624 BORDNIR FLowER
_
31 r. 1
•
..
4,1
I 0 1.1 1.11 I :1 1 1 11 1 .., : 1.1„h,
122 DEE,F\0 41 6:17 E-313RONIA FLOWER VOLA1 ILES
. ChL:1C320
--219 —4(3
1
1
j0 711 32i
tt, JJ 14 I 1111, d ,1, 14 P :rrt r 320
DEBRO4 G8B ri I Y T LIRE: CRL: 1C300
MASS SPECTRA 03—DEC—RP
MIXTURE TETRAHYDRCNAPHTHALENE AND A D1METHYLINDANE CPO. (Peak 80 21:41
-
100 '200 302
- 169 -
„r METHYL - NAPHTHALENE (Peak 9)
1200 322
0EBR0 736 BORONIA FLOWER VOLATILES c5L:]casa
METHYL N DECANOATE (Peak 10) 23.12
100
DEBF:04 750 DORON I R FLOWER VOLAT I LES cp.L:Icaoa
UNKNOrIN
411
122
-
69
T.;
1 7.00 .;00
03-DEC- Zj.217,
16382
SS0
11328
1216
1 IN
DEBR04 70S cRL:Inera
1 47
111
4! 1! rj I. VA
100
BORON! A FLOWER
1 320
03-DEC,-(3 zz:13
' F
VOLH1 I LF.S
- 170 —
MASS SPECTRA
: •
MF_NTFONE (Peak 8)
! H! 1
7.4 ! 1 I 1 :".,•,: l
'. 1 I It :• I I
il :•,',1 I
.- 11 1 1 III 'II r
' 4I1 II . 1 .111 A. C.: II, 1 . , 1 4 1.
—1 ''''. , i r T , T•
Goa BOROW1H FLOWER VOLRII.LE 03 — DEC--&i. 1
NAPHTHALENE (Peak 8a)
C'Ftc c7
:fL :
-.- i ii 1 : H t
• 1 . i t i t H ...
I 1
DEBRO4 CP.L:Ic3so
-
,
-
,
,
- I I i
P.J1 1...b..r1,4,46-1..g..wiJ........I.J1 !.''' ..._—_, , .g.,.._,. ............i...._. ...!. t 1 —T r -r--------------r
'1. aa Z.'i'l 7.:63CI
D F2 ' G3 cr S2F,.[Its: CrIL::C1420
• : `• 2.• I I 1 i
i 1 1 Z " 11
2 1 1 I
1 1 I I 1 1
,-,•; • 1 ! I 1
-,
.-.=1 J 1 , , , ! I i .: .gg... ,.., .g ..,.....„:„...,,,a,,,,...„..,,,.. i...... f I i II.II J.I.I i .,.. ,),1_,k, 1; gl
- - 'g
9.2 Unknown Aromatic cpd (Peak 8h)
L, • 222
L.:c_n;--•,b4 617 FOR0r:IR FLOWER, voLAULEI.:; D E C ChL:ICa,08
Unknown compound
I !!
li '.... ...
Efi
/H
I P! ; • I ; ! I I .1
! 1 II 41 • ! r • 'T -I -4
.
:7:3 ZOO
617 BORON' A FLOWER VOLAT ILES
141 1. 111 ;
r
GEER04 S7c; CRL:Ic2no
41
f's5
1
— 171 —
MASS SPECTRA
EOF,r, ■.! Ft FL-OWE:F-3 %/CV Lt.::
PCJITHONE (Peak 8) a _
382
03—DEC-80 le.s5
2181
. I AJill 1
188
DEBR04 600 BORONIA FLOWER VOLATILES CRL : 1C389
NAWTHALIFTE (Peak 8a)
03—DEC—P0 1R:C
83
ii
41
, Ike/ [! 11..11 41, d.,_;to. , ,,.. .i. • L IL I { till
L .A. ,
2351
a .
120 ZOO 300
DEBR04 604 BO-FON:A FLOt4E.R VOLR1 -ILES ChL:Ic322
9 Unknown Aromatic cpd (Peak 8b)
03—DEC-80 1 3
91
1359
280
03—DEC--;20 13:27
1 —T
102 200
Unknown compound
GS1
! 47—
--T 32
ZOO 7100
41
I DEBEi24 7Sc1
L.
2e,4.
2Tir
e N,E .) I --r --r
100
BOFON]R FLOWEli vOLAT ILES
11,11 , j 1. 3, I IIfa I IL, II! ft :2•13
0E5R84 688 mix1ul9E-cRL;Ic20o
- 173 - MASS SPECTRA
MIXTURE TETRAHYDRONAPHTHALENE AND A DIMETHYLINDANE CPD..(Peak 8c) 21:4:
1216 -
1
1 _
I 1
'1 ' I
1!1 I, .1 i, 0
I ,
,, , i I
'1!T I
4 0 . ..i. r— T -1" -----r 1 ---1;
9FBR84 7O 0FiGNIFI. FLOEF VOL.HTILL:-.; caL::=32o
METHYL NAPHTHALENE (Peak 9)
,4
Ii 328
1,1 , 1i ,T.1
'10.2 aeo 300
DEBR84 736 aoRor4: FLowER V.ht ILL; criL:Ic302
METHYL N DECANOATE (Peak 1 0)
03—DEC 23212
1G3130
•
;ov
SSi3
1-70.0
:00 200
100 2:10 32o
220
03-DEC-%i.0 19:27
202
Unknown compound
DEBR (aq CRL:1C390
_1
- 174 —
MASS SPECTRA
S74 50soNIA FLoLIER VflLf-U Li-
MENTI-JNE (Peak 8)
NAF1-fTHALENE (Peak 8a)
03-DEC--) 19:G
0EB1904 GOO BORONIfi FLOWER VOLATILES Cf211_:1C3138
1
44
Z3S1
.1 •,.,I _1 .
4 1
DEBR24 604 6 OFiONIF1 FLOL4ER VOLFil ILES CW— :1C999
Unknown Aromatic cpd (Peak 8h) : 1 4
31 7, 1
ass
.;
1/ 1 .1 I . t i , pc.,1 .. • '•
149
15 4
I
03-DEC-80 13tZ
DEBRect 617 .BOROtil A FLOER VOL_Fri I LES ChL:1C1400
r 3 ? - c.
21 119
cinti, 3.1 1.,11 11 ,4
I .;
1 90
21 84
6S1
h , JI. 200
100 ZOO 30.0
;20 03—DEC—E.
2.00 !oo 0EER24 7S0 EC3P,01 ,1 .19. FLOWER VOLHT ILES
SSD
'30:4
111
1 111 1 I I I iNi,ItOthi 10 1 P 11- 1 100
if , A ITti, A , 1 !1
DEBR04 736 BORONIA FLOWER VOLR121..E1:: CrL: 1C2
_71 METHYL N DECANOATE (Peak 10) .
g3—DEC—e.? 23,12
16300
CIL: 1C3
- 175 -
DEBROg 68E3 nixTURE-cRL:Ic300
VASS SPECTRA 03—DEC-20
MIXTURE TETRAHYDROVAPHTHALENE AND A DIMETKYLINDANE CPO. (Peak 8c) 21:41
171
44 47 1E2 .11
1; [I .1
100
DERRa4 72 ORON2 VOL:IT 1 Li7.
1
1 I
-1
320 03—DEC—FIP
METHYL NAP1-MIALENE (Peak 9)
11 328
03-DEC-80 18:6
DEBR04 S74 BORONIFI FLOWER VOLATILES'
MENTHONE (Peak 8) CRL:1C200
1
2010 200
03-DEC-80 18ASS
F
2184 41
SS 63
'3
1'1 83 97 14
. I
cc,
ive3
DEBR04 600 BORONIA FLOWER VOLATILES CML:1C300
2114
44
444.11,14 _ 100
2351
7 —W
200 200
NAPHTHALENE (Peak 8a 128
MASS SPECTRA
DEBR04 604 BORON' A FLOWER VOLAT ILES CRL:1C300
03-DEC-80 19:2
Unknown Aromatic cpd (Peak 8h)
•
es,
1959
91
41
1 i 1 I
• I .---- .....I.J.-..- -.-.4-,,wir...,
100 0C3
20 DEBRO4 617 BORONIR FLOWER VOLATILES
03-DEC-BO
CHL:1C300 Unknown compound 13:27
1 kNr
1 -1
1 1
11
,
1 a 1 0
lb 1111 01111
71
ift
91
ti k L Li 1 • 8
till..
6S1
100
200 00
DEBR04 688 MIXTURE CHL:1C3130
03-DEC-80 MIXTURE TEIRAHYDRONAPHTHALENE AND A DIMETHYLINDANE CPD. Peak 8c) 21:q1
100 12130 -T- 300
MASS SPECTRA
i1
ii
S4 1
,
1
118 131
10
1216
1 11328
100 200 202
DEBR04 70S BORONIR FLOWER VOLF1T ILES
METHYL .NAPHTHALENE (Peak 9) CV/ 1,4
•
03-DEC-80 22:13 CaL:1C300
CZ
at)
64
CS.■
METHYL N DECANOATE (Peak 10)
40
DEBR04 73e BORONIA FLOWER VOLATILES cfiL:1c3B0
Igo 200
DEBRO4 7S0 BORONI A FLOWER VOLATILES criL:Ic-3oo
UNKNoWN
03-DEC-80 Z3:12
16380
03-DEC-8011 2.2:38
■-■
I
_
4' SS0
4 G9 -
'VI
-
2 1 1
-I
I l
100
200
300
DEE3R131- 8S8 BORONIR FLOWER VOLHT ILES CAL:IC30
03-DEC-80 27:2 P.-IONONE (Peak 18)
zoo 30 0
FWOJ OFCLIRM
DIHYDROACTINIDIOLIDE (Peak 20) 1_
\
IL
736 z
i.1 S7
1 1 ,
1 - 7
71 1?
t T 11 . .---...--....---.,
et3
c'D
4:1
8836
200 200
03—DEC-80 c8 27:SG3
1'77_
100
DEBRO4 883 BORONIA FLOWER VOLATILE cmL:lcam
- 181 -
1JE1036 92 PROSTRNTHERA LRSIFINTHOS °Vial 50-2404 CRL:10488 UNKNOWN
7
20-APR-82 2;54
180 ;■ .200 0E1036 117 PROSTRNTHERFI LFISIFINTHOS OV101 50-240 4
L:10480 STR: E. UNKNOWN 4
388 20-APR-82
3142
149
180 7-288— - 300 .
20-APR-82 3.S3
DE1036 123 PROSTFINTHERA LRSIFINTHOS OV101 50-240 4 L:10400 4 METHYL-PENT-1-EN-3-ONE
cc
27
942
380 20-APR-82
108 280
DE1036 1S3 PROSTFINTHERR LRSIANTHOS OV101 50-240 4 CRL: 10480 STR: E• UNKNOWN cc
4:S8
18S
40
- 182 -
0E1036 161 PROSTANTNERA LAS 1 FINTHOS OV101 50-240 4 20-APR -82 L:10480 STA:E. UNKNOWN s.s
4'4
1149
7
- - - , - 102 208
DE1036 166 PROSTANTHERA LAS FINTHOS OV101 50-240 4 CAL:10400 STR:E. UNKNOWN
4.4
• • 308
28-APR-82 5.14
) „J
574
4
2
a
1 00 208
0E1038 189 PROSTANTHERA LAS I ANTHOS OV101 50-240 4 L:12480 STA:E. UNKNOWN
20-APR-82 S :57
54
Id !IL J I
100 208 0E1036 243 PROSTANTHERF1 LASIFINTHOS OV101 50-240 4 CAL:10480 STA:E. PENTYL ESTER
ROB
20-APR-82 7.29
100 202 390
BENZALDHYDE •7
2 - 106
CAL:18460 STA:E.
2S8
4,1 107
542
121
,,. 1 , 11.1.1, , . 11. 100 200 300
- 183 -
0E1036 250 PROSTANTHERA LRSIRNTHOS OV101 50-240 4
109 DE1036 254 PROSTANTHERA LRSIRNTHOS OV101 sp-ate 4
L: 10400 STAE. c‹, -P 1 NENE
20—APR-82 7:S3
Jt_ J J - 1
1
-
108 288
300
I - C. C. C C
DE1036 267 PROSTRNTHERA LASIRNTHOS OV101 50 -240 4 L:10400 STA:E.
CAM PH ENE
22—APR-82 a.zs
4. 1" — 1 1
102 288 388
DE1036 296 PROSTANTHERR LASIFINTHOS OV101 50-240 4 22—APR-82
2163
41
G3
1
CAL sTA:E. :10480 9:29 -P I NENE "13
— 184 —
•20—APR-82 9144
meesaas PROSTANTHERA LASIANTHOS OV101 50-240 4
CRL:10480 STA:E. MYRCENE 4
189 /.289 0E1036 327 PROSTANTHERA LASIANTHOS OV101 S0-240 4
C1L:10408 STR:E. —PHELLANDRENE
- ---- - - - - 388
20—APR-82 10:18
•
664
20—APR -82 10126
DE1036 331 PROSTANTHERA LASIANTHOS OV101 50-240 4 CR1_:10408 STR:E. CYMENE MIXTURE
ct
4
111 1 189 - I :---- • -
228 - - -
CHElEr3G; 344 PROSTANTHERA LASIANTHOS OV101 50-240 4 CAL:1E3400 sTR:E. 1,8 CINEOLE + CYMENE
1 51
L ik iIJt
352
^-1 — - r
20—APR-82 101 S2
a
2132
134
k. . 100 209 390
4.1
-185 -
20-APR-82 11:11
0E1036 3SS PROSTANTHERF1 LASIRNTHOS OVi 01 50-240 4 CF1L: 113490 STR: E. UNKNOWN
4a
1.9
406S
■-•
, 203 360
7
34
IJI
DE1036 394 PROSTANTHERA LASIRNTHOS OV101 50-240 4 20-APR-82 L: 10490
SIR: E. UNKNOWN MOMOTERPENE
12 .24
136
216
-1 - I I 260 3es
C C.
0E1036 404 PROSTRNTHERA LASIRNTHOS OV101 50-240 4 20-APR-82 CAL:IC/400 STR: E.
CIS LINALOOL EPDXIDE 12143
302
100 200 0E1036 420 PROSTRNTHERA LASIRNTHOS OV101 50-240 4
L:10490 STA:E. TRANS LINALOOL EPDXIDE Sc1
7
390 20-APR-82
13.14
a 4,1
132
s- -r 220
IJ
44
27 41
S'
84
t % 100
274
L 200
308
- 186 -
DE1036 437 PROSTANTHERA LASIRNTHOS OV101 S0-240 4 CRL:I0408 STA:E. L INALOOL 71
1100 0E1038 458 PROSTANTHERR LASIFtNTHOS OV101 Sle-;240 4 CRL: 10408
STR:E. UNKNOWN
- - ka1114- .1i .....
20-APR-82 13:46
784 •
-
398 20-APR-82
14125
100 •-••-•-•-•-•"1-•-• I - I
288 388
DE1036 460 PAOSTANTHERA LRSIRNTHOS OV101 S0-240 4 20-APR-82 CAL: 10400 STR:E. 14129
UNKNOWN Ft4
245
I , 180 288 288
0E1036 492 PROSTANTHER8 LASIANTHOS OV101 50-240 4 20-RPR-82 CAL: 10.408 - STR:E. CAMPHENE HYDRATE is,zs
4'4
4.1
3f.
20-APR-82 1S.43
0E1036 499 PROSTRNTHERA LRSIRNTHOS OV101 50-240 4 CAL:10488 sTR:E.
PINOCARVONE
' 0 ,
20-APR-82 16.11
1119
DE1036 514 PROSTRNTHERF1 LRSIFINTHOS OV101 50-240 4 CM:111400 STR: E • ARCHILLINOL (?)
s-4
388 20-APR-82
16.4S
1013 288 DE1036 532 PROSTRNTHERR LRSIRNTHOS 0V101 S0-240 4 CM:113480 SIR: E• TERPINENE-4-01
- 187 -
ea
2
e■—•
4
II r , . ,,_,u1 -
200 100
3SS2
33
86
.4
Z7
0,, ,,,,,„I. loik
,. 4 288 DE1036 SOS PROSTRNTHERR LRSIRNTHOS OV181 50-240 4 CRL:10488 STR.E.
27
208
UNKNOWN 4
•
288
28S
388 20-APR-82
is.s4
100 , 2013
DE1036 574 PROSTRNTHERA LRSIANTHOS OV101 50-240 4 CRI-:104021 STA:E. UNKNOWN
ctc
a
2 41 so
acao 20—APR-82
18:4
2-42
4854
43
93
I 121 3G
100 209
35
T Li
ISO
^ —
- 188 -
0E1036 548 PROSTANTHERA LRSIRNTHOS 0V101 50-240 4 20—APR -82 L:10400 STR:E. • TERPINEOL
17:IS
DE1036 577 PROSTRNTHERR LASIANTHOS OV101 50-240 4 1L: 10409 STR:E. UNKNOWN
20—APR-82 18110
215
STA:E. CARVONE
4
3r
"1-11 J111 - 0
DE1036 584 PROSTRNTHERR LAS1ANTHOS OV101 CAL:1[1400
-r 200 390
50-240 4 28—APR-82 18.23
971
8
20.
300 100
C - a
J
- 189 -
aa
0E1036 592 PROSTANTHERA LASIRNTHOS OV101 50-240 4 cAL:1o40e STA:E. UNKNOWN
54
it 1111, 100 -60
DE1036 603 PAOSTANTHERR LASIRNTHOS OV101 50-240 4 CFIL: 10400 sTR:E. UNKNOWN
20-APR-82 18:38
v. - -- e 308
20-APR-82 tsgss
6 -
121 a
00
27 150
till &at, 100
DE1036 GSS PROSTANTHERR LRSIRNTHOS 0 1/101 S0-240 4 cRL:104e0 STR:E.
I SO-BORNYL ACETATE 4-4
les DE1036 661 PROSTANTHERA LASIRNTHOS OV101 50-240 4
L:10400 • STA:E. UNKNOWN
./
200
I I I I T
ape 20-APR-82
20.4s
388
20-APR-82 28:37
322
2 - 43
3sa
109 2130 388
- 190 -
. . .
0E1036 670 PROSTANTHERR LASIANTHOS OV101 50-240 4 CRL:10480 STR:E. THYMOL
,
20-APR-82 21:5
13S
215
150
• I 1 - •- --- i• - I lea
13E1036 714 PROSTANTHERA LASIANTHOS OV101 S0=240 4 CAL:10400 UNKNOWN
4'4
TJ • -
380
20-APR-82 22=23
138
04 40
••••••" r•-• • ^' 'V • - - -
— — 390
-
• 0 0 • :
0E1036 719 PROSTANTHERF1 LASIANTHOS OV101 S0-240 4 20-APR-82
UNKNOWN CRL:10400 sTA: E 22:38
c7 181
1 I '
1 ''''•"•1 1 - ' -1 "
1 00 ---200 - 380
0E1036 76S PROSTANTHERA LASIANTHOS OV101 50-240 4 20-APR-82 L: 10498 • STA:E. UNKNOWN 245
7 496
132
Sr
HAL LA.
qpi 1,1 I g A _LAII 100 2B2
STR:E•
1 (
I,,,) 100 200
PROSTRNTHERA LASIANTHOS OV101 50-240 4 UNKNOWN
93 1137 133
121
100 -
208 380
20—APR-82 26:28
0E1036 841 PROSTANTHERA LASIANTHOS OV101 50-240 4 CAL: 10489 STR:E. UNKNOWN
100
GS
69
.acta
204
187 202
200
r -1 1t4L,
0E1036 823 CRL:10400
41
133
S37
161
204
280 320
0E1036 864 PROSTANTHERA LASIANTHOS OV101 50-240 4 20—APR-82 CAL: 1E1400 STA:E. UNKNOWN 26,s3
121
C — C
4.1
91
119 1 133 59
147
-
300 20—APR-82
WsS4
104
187
161 204
4
PRDSTANTHERA LASIANTHOS OV101 50 -240 4 STfl: E. UNKNOWN
o g -
0E1036 897 CRL:10400
308 20-APR-82
28s14
107 121
93
- 192 -
0E1036 857 PRDSTANTHERA LASIANTHOS OV101 50-240 4 L:113400 STR:E. UNKNOWN
20-APR-82 26.68
4) 1SS
27
L. 100 208
0E:1036 881 PADSTANTHERA LASIANTHDS OV101 50 -240 4 STR: E. CAL: 10488 UNKNOWN
•
I' r 300
20-APR-82 27&6
149
308
DE1036 Eaa PROSTANTHERA LASIANTHOS OV101 50-240 4 CM:111480 STR:E. UNKNOWN
20-APR-82 28.1
161
209
IL 699
7
121
41
107
4 7
SS
'300
214
308
161 189
?
134
- 193-
CAL: 11)408 .2ROSTANTHERA LASIRNTHOS OV101 50-240 4 sln:E. UNKNOWN c
20—APR-82 29:41
105
DE1036 960 CRL:1D488
PAOSTANTHEAA LASIANTHOS OV101 50-240 4 STR: E. UNKNOWN
• 390 20—APR-82
30.13
114
288
20—APR-82 30=24
0E1036 966 PROSTANTHEAA LASIANTHOS OV101 52-240 4 Cf1l.: 1E1480 STR: E • U NKNOWN
4'
111
172
LL.1,
0E1036 978 L: 10488
41
AJJ 11.11 1.41 J. 1 t tL___ , . 188 .288
PAOSTANTHERA LASIANTHOS OV101 50-240 4 STR:E. UNKNOWN
4-4
3 -
r 398
20—APR-82 3014?
2888
34
UL
101
208 388
644
11 1
!,-„J I
- 194-
20-APR-82 -
DE1036 981 PROSTANTHERA LASIRNTHOS OV101 SO-240 4 CRL:10488 STR:E., UNKNOWN
4q.
41
159
, I 1,40, , ,L1)01,11it, JILL
, Lik
100 200 0E1036 38G PAOSTANTHERA LASIRNTHOS OV101 50-240 4 CAL: 10480 STR:E. UNKNOWN.,„.1
4:1
334
PA' Orb
161
„gm
G9
109 ----- — - - • -
200 390
a r •388
20-APR-82 31:2
•
DE1036 993 PROSTANTHERF1 LASIRNTHOS OV101 50-240 4 20-APR-82 CAL:117488 STR:E. UNKNOWN 3115
41
188
DE1 eras 1002 PROSTANTHERA CAL: 10480 STA:E.
2 41
LASIANTHOS OV101 50-240 4 20-F1PR-82 31:32
LEDOL 66S
1 ,300
100
149
- 195 -
DE1038 1007 PROSTANTHERA LF1S1ANTHOS OV101 50-240 4 20-APR-82 alt.: 10400 STFt: E. UNKNOWN
31142
4-4 203
41
107 a"
•I tot. ,
200 0E1036 1019 PROSTANTHERR LAS1ANTHOS OV101 50-240 4 CHU 11)408 sTR: E. -EUDESMOL
- ----- ----r 300
20-APR-82 32:4
100 200
— 196 —
DE1030 176 RADIATA BARK OIL CW2OM SO-200 DEG CRI.:1C3S0 STR:E. CAMPHENE
-0 19—JAN-81
. 61S
191
638
a - en
67
41
a
200 DE1030 226 RADIFiTA BARK OIL Cw20m S0-200 DEG CRL:1C3S0 sTR:E. PINANE ? .1c
320
19—JAN-81 7g48
408
6-7
138
- 100 200
en - g 300
1403
100
DE1030 231 RADIATA BARK OIL C12OM SO-200 PEG CAL:1t2S0 sTA:E.
3 CARENE
200 ' '300
390
1236
39—JAN-81 7:se
ct-1
DE1030 228 AROIATA BABK OIL CW20M SO-200 PEG CRL:1C3S0 STA:E.
UNKNOWN O ./
19—JAN—E l 7:SZ
- 197 -
0E1030 240 RADIATER BARK OIL CW20M SO-200 DEG cm:Ic3S0 MYCRENE
19—JAN—B1 817
100 200 300
0E1030 249 RADIATR BARK OIL CW20m S2-200 DEG 19—,M-81 CAL:1C3S0 STA:E. CYMENE (TYPE) s
ssts
91
—„Ia l 200 ' 300
-r
DE1030 2S7 RADIATA BARK OIL cw201 SO-200 DEG cm:Ic3s8 s1n: E. LIMONENE
13-JAN-B ]
8:52
1433
IL ,
0E1030 2S8 CFIL:IC3S6
L j • " " I • I
UNKNOWN
100
300 19—JAN—G]
8:54
100 zoo RADIATA BARK OIL cw20m SO-200 DEG STR:E.
2473
200 300
- 198 -
DE1030 271 RAD] ATA BARK OIL CW2OM SO-200 DEG cm:Icase STR:E.
g3 DODECANE
19-JAN-81 3.21
43 811
ro0
4
100 200
0E1030 273 RADIATA BARK OIL CW20M SO-200 DEG CRL:1C3S0 STS:E. PHELLANDRENE
300
19-JAN-81 9.2S
1920
,
-r 200
100
300
300
DE1030 278 RADIATA BARK OlL CW20M SO-200 DEG cm.:Ic3S0sTR:E. UNKNOWN
4'1
7
100 200
0E1030 313 RADIA1 A BARK OIL cw2er1 S0-200 DEG CRL:1C3S0 STR:E. M CYMENE
19-JAN--e) 9:3S
207
19-JAN-81 10:47
597
200 300
100
100 DE1030 371 ARDIRTA BARK OIL CW2OM S0-200 DEG
MYRTENOL
100
1 9-JAN-21 12:q6
353
137
152
200 300
CRL:1C350
- 199-
0E1030 321 RADIATA BARK OIL CW2OM S0-200 DEG CRL:1C350 STR:E.
io-CYMENE ils
19-JAN-81 11t 3
3970
101
134 911
100 2 I 1 1
00 300
DE1030 329 RADIATA BARK OIL CW2Om SO-20O DEG 19-JAN -81 CAL:1C3S0 STR:E. TERPINOLENE 11:z0
1?1
1039
136
200 300
100
1 9-JAN-2 2 12:1
DE1030 349 RADIATR BARK OIL CW2OM S2-200 DEG GRL:1C3S0 STR:E. C
13 HYDROCARBON + UNKNOWN
43 196
4
-
200 300
- 200 -
DE1030 396 RADIFITA BARK OIL CW2OM S3-200 DEG alL:Ic3se STR:E. UNKNOWN MIXTURE
19-JAN-8I 13,37
119
573
41
67
300 100 200
DE1030 397 RADIATA BARK OIL CW22M SO-200 DEG CRL:1C3S8 STR:E. UNKNOWN
19-JAN-81 13,40
719 `17
67
)61,,Atik tiN 11-
108 200
DE1030 403 RADIATA BARK OIL Cw20m S2-200 DEG CRL:1C3S0 STR:E.
I CYMENE (TYPE)
41
ig 300
I 9 - JRN-R 1 32:C2
327
13h
) ti )11 lilt 100 200
DE1030 416 RADIATA BARK OIL Cw20m S8-200 DEG : IC3S 0 SIB: E. UNKNOWN
100
300 '1
19-JAN-2, 14,13
137
953
kh r
200 300 T
188 200
DE12/30 438 RADIATA BARK OIL CW2OM SO-200 PEG cAL:Ic3S0 STA:E. FENCHONE
380 19—JAN-81
1514
69
41
1184
-[
100 200 388
- 201 -
923
DE10304E36 RADIRTA BARK OIL CW22M S2-200 DEG CRL:1C3S0 STR:E. -DIMETHYLSTYRENE
19—JRN-8 16e]
9
100 220 0E1030 481 RADIATA BARK Olt_ CW2OM SO-200 DEG CRL:1C3S0 STA:E.
474 UNKNOWN
19—JRN-81 16:32
132
4 67
10P Zeo 300
132
17
—
BORNYL ACETATE DE1030 430 RAD1ATA BARK OIL CW22M SO-200 DEG CRL:1C3S0 STA:E.
19—JAN—B] 14147
249
- 202 -
DE1 H30 484 RADIATA BARK DIL CW2Eiti S0-202 DEC CRL:1C3S0 STA:E. UNKNOWN
19—JAN-81 10:38
94
103 67
100
9.1
200 0E1030 435 RAM ATR BARK OIL C1420M SO-200 DEC CRL:1C3S0 STR:E. UNKNOWN SESQUITERPENE
9
htt -
300
19—JAN-81 • 17.1
167
10S 42
t iAiiLJ;
200 '300
14
19—JAN-83 17,1s
DE1030 S02 RADIATA BARK OIL 0,420m S2-2oe DEC CAL:1C3S0 STR:E. UNKNOWN
9 1194
41
-1/1'• I , 1100 200
DE1030 518 RAD I RTA BARK OIL Ct-120m S0-200 DEC CRL:1C3S0 STR:E. COPAENE
IS1
- f 300
1 9—JAN-8 I 17:46
176 IOS
:Ma
81 136
I I I I1 II I r ti 100
2/4
200 300 Jk I
1111IFerliptfl ,
Z t
Set
9ZZ L ti
NMONNNn snid 3NDJAKS1AHEWIO '3:W1S escatrwo 030 00Z-OS WOZti3 110 )1i,11,18 171113101:m ES @E0[30
8S:L 18-Ntjr-61
, 00Z , 00Z t
ii 00t
tZt
1
9
OtoS EG
E3'GE 1001VNI1 esEDE:114.3
930 0e2-0S 140?-113 110 Eat:i IOLIEI 6LS 0E0130 00E 00Z 00I
t ES
8Z9
5b:gi
--3-Nyr-6 3N0HdWV3ONId '3:141S OSE31: -IF.10
930 013Z-OS WeCti3 -II 0 )402E3 w1t4I0uld SLS 0E0130
00E 00Z 001
a
tb • SS
Zs:ec • 8-NUC-6 I
OBE
3N0HdWVOONId OSI OSE31:1U3 930 00Z-OS 140Zt13 110 matga ult:110b1U 6125 0E0130
eoz eet CLI
1
DE1030 S88 RAD1ATA BARK OIL C1420m SO-200 DEC cRL:Ic350 STA:E. UNKNOWN SESQUITERPENE
79 41
1 8 200 300
19-JFIN-83 20:28
DE1030 S96 RFiDIATA BARK OIL Cw20m SO-200 _NKNOWN
DEG CFIL:1C3S0 STR:E. U
300
19-JAN-81 20:32
100 ZOO
DE1030 601 RRDIATA BARK OIL 042011 S3-200 DEC CRL:1C3S0 STR:E ISO BORNEOL
450
14- ‘3.38 200
- 204 -
19-JAN-8) 20.12
279
94
.
A loll lb cAL:Icase STA:E.
109
133
300
19-JAN-81 • 202G
L -
DE1030 S9S RADIATA BARK OIL DU2OM SO-200 DEG
UNKNOWN
011 8
c 7
S'A
-21S2
41
135 ige
•204
4S9
108
41
" I T
1 9 —JAN-431 • 20.SS
19—JAN-8 2 20:S3
DE1030 GO8 RADIATA BARK OIL Cw20m 50-20O DEC CAL:1C3S0 STA:E. FENCHOL
41 89
107
STA:E. UNKNOWN CAL:1C3S8
19—JAN-81 21:s
0E1030 G14 RADIATA BARK OIL 0-120m S2-200 DEC CRL:1C3S0 SIR:E. 6 TERT. BUTYL CRESOL
- 205 -
200 300
4 SS)
164 —
.,-Ps cht. Rif , L 1 • I
I
100 610 DE1030 G22 AADIATA BARK OIL Cw20m S0-200 DEC caL:Ic3se STA:E. UNKNOWN
71
100
•1/41L A 188 208
DE103F3 G439 RADIATA BARK OIL CW2OM SO-200 OEG
200 300
4
300
19—JAN-81 21:22
100
1771
3303
CHL:1C3S0
leo . zoo DE1030 G62 RAD1 ATA BARK OIL Cw20ri S0-200 DEC
STF1:E. UNKNOWN
27
107
IS O 1 3 S
s r - 300
3 9—JAN-8 : 2244
64 3F.
1114
100
--r
200 3 r 00
200
- 206 -
DE1030 G28 RADIATA BARK OIL Cunti S0-200 DEC CRL:1C3S0 STA:E. TERPINENE-4-ol
71
I 9—JRN-8 21:34
923
4
,114..),LL
108 220
DE1030 G44 RADIFITA BARK OIL Cw20m S0-200 DEC
•• 300
1 9-3RN-8 1 GFIL:1C3S0 STR:E. 22s7 UNKNOWN 9
' 197 41
44
*
DE1 030 GS1 RRDIATA BARK OIL C42gm S0-200 DEG CAL:1C3S0 STA:E. MYRTENAL
IS—JANJ--Efl 2221
3
r100 200 r
300
DE1030 672 RADIATFI BARK Oil_ CL-120ti S2-200 DEG L:1635ø STR:E.
UNKNOWN 19-JAN-82
23.4
BORNEAL PLUS UNKNOWN ctc
CAL:1C3S2 STA:E.
—207 —
276
• 41
134 Ga
g-
. 1141 rodtiviit. J J I ,
I
S.
302 100 200 DE1030 683 RADIATA BARK OIL CW20M SO-200 DEG 19-JAN-81
23.27
527
'
100 220 300
DE1030 631 RAOIATA BARK OIL CW2OM SO-200 DEG CAL:IC3S0 STA:E. UNKNOWN
19-JAN-81 23.43
•
317
.4
41. 67
217 Ji
'TB
1 Alit 11 1 L1I i,,t 4,1 I 300
19-JAN-81 24.0
100 200 0E1030 699 RADIATFi BARK OIL C1420M SO-200 DEG CAL:1C3S0 STA:E. UNKNOWN
37
1' 2
k t1
300
41
81
ii
161
2134
Lid Ii1JJ1J1111
300
100
200
121
81 136
11 illitj.k 300
19—JRN-81 24:S9
S4
*4
- 208 -
DE10313 714 RADIFITA BARK OIL CW2Bri Se-200 DEG CAL:1C3S0 STA:E. .=c-TERPINEOL
19—JAN-81 24.30
2676 cq
208
0E1030 728 RADIATA BARK OIL CLI2Ori S0-200 DEG CAL:1C3S8 STA:E. MUUROLENE
130
DE1030 730 RFIDIATA BARK OIL cw20;-, S0-209 DEG CAL:1C3S0 STA. UNKNOWN
1 ,1
41 383
67
2-7
1j II 111 II_ 1_01111i 100 200
0E1030 74S RADIATA BARK OIL CL-120m S2-2kle DEG CAL:1C3S0 SIA:E.
UNKNOWN
3
300
3oe
gre V
- 209 -
c3E0:313 7SS RADIATA BARK OIL CW20m SO-200 DEG
19—JAN-81 CRL:1C3S0 STR:E.
CADINENE 2S SS
est
!ys 134
24
377
100 200
0E1030 7se RADIATA BARK OIL CW20m SO-200 DEG cRu1c2s0 sTH:E.
UNKNOWN 7 ;6 ..
300
100 230
I 9—JAN-81 26: 1
21
,
0E1035 774 RADIATA BARK OIL CW20m SO-200 DEG CRt_:1C3S0 STR:E. UNKNOWN
394
120 0E1535 75S RADIATR BARK CRUIC3S0 STR:E.
200
OIL CW20m SO-200 DEG
-11 300
19—JAN—Si 2g:SG
UNKNOWN . 147
—5 300
220
- 210 -
0E1030 787 RADIATA BARK OIL CW2Ori SO-200 DEG CAL:IC2S0 STa:E.
. , ,
g 1
:;) el • 4 la
I
! , i
oi ii
Li, VII AL III!II1L ii0iii jIi ili I1 ii ,ii , i
-1- . r- r 1-- —1--- : I00 200 :300 0E1030 79E AAD1A7A BARK OIL Ct--120m SO-200 DEG 9—JFN-81 GAL:1C3S0 STFI:E.
1
,7, •I I i
.7! • t
, 1
.• , : , ; I,
H I'
■ ;
1, , • '1 1 , i ■ • H ■ j ill II! il, r' I i i
1 t i
, • ■ j;" 11 •Ii[ •ViL, i1444,111k,, A l;',ill„ IL . :11 14 ;III ii, '.'lj
1 I
! -1--- T . r ---,' 100 2en
CET:1032 21 S RADIATE: BARK OIL Ct-r.?.Ori Se -20o, DEG
I 3-3FIN—S1 caL:la3So STF1:E. CALAMENENE
26:e
UNKNOWN 2'7:0
103
UNKNOWN 27:17
•
ISIS
el•
6G2
.• 1 , rt ;
;
,
!
„ • r...._J.._ • ; j • , ...T ..44, - • ,...,:._,..„1-.4„ , I , . ih, •, Al!: 4 , . 4- . r , ---T— r f--- -,i
3oe 200 :100 DE10,10 8?S' RAD!PTA:--.3AFic 07L 1:::--1201 BC 2G DEG 33 - 3RM-1731 cpL:lc2so s7H:E• 28:2S UNKNOWN
2SZ
•1
ri
‘1 ,1
'' .i :. 'l id .:'• : '' .'. 1 1, '', i ', •
, ..aLiL'::421.1L2.4 111 1 .i!Litit... , q-u0IL ' : I I ' 1 :.`.' • i i ..'. I, • II., I : j l', ; ' ] '1,1 .',1'01 • ill :IVIIII
1 III di11 .1 1 : .:LIL ■
".'•,'; , ; i ' 1 •
'100 300 --r
7 1
10
I • 1
200
126
^
•4
0E1030 906 RADIATA BARK OIL CW20m SO-200 DEG 19 -JAN - 81 31:5
162 1 SO
CAL: 1C30 SIR: E. UNKNOWN I 37
100 200 0E1030 916 RADIATA BARK OIL CL-120m S0-200 DEG CAL: 1C350 STR:E. UNKNOWN
S.
100
19—JAN-81 31 :2$
- 211 -
0E1030 840 RF1DIATA BARK . OIL CW20m SO-200 DEG . CAL:Ic3s0 sTA:E.
P-CYMENE-8-o 4 "4
19—JAN-81 • 2843
2510
13S
....yrj I I 100 200
0E1030 852 RADIRTR BARK OIL CW2ON SO-200 DEG CRL:1C3S0 STR:E.
1 OR UNKNOWN
114
1 '1 300
19—JAN-81 23.14
•
CD
S.
300 '
160
0E1030 962 RADIRTA BARK OIL C1,120t1 S0-208 DEG CRL:1C3S0 STA:E. UNKNOWN
R-7
93
3 .41
1 1
0 1— 100 200
DE1030 1053 RAOIFITA BARK OIL C42011 S0-200 DEG CAL:1C3S0 STA:E. UNKNOWN 1s
41
-
27
Ii
19—JAN-81 33 , 0
iaa
,aeca
19—JAN-81 36,7
200 300 100
'300
270
200 100
- 212 -
DE1030 1061 RADIATA BARK OIL Cw221m SO-200 DEC
19—JAN 81 CAL:1C3S0 STA:E. UNKNOWN
-36:24
A TECHNIQUE FOR THE SAMPLING OF VOLATILE ORGANIC COMPOUNDS
R. B. (Bob) Chesterman
R. (Bob) Chesterman, currently engaged in analytical and development work in the Department of Environment Laboratory in the Chemistry Department of the University of Tasmania, P.O. Box 252C, Hobart, 7001, Tasmania.
INTRODUCTION The sampling of volatile organic compounds has been undertaken using a wide variety of techniques such as cryogenic trapping', liquid adsorption 2, solid adsorption' and chemical reaction. Each technique has inherent problems associated with either the collection of unwanted material, such as moisture, or the quantitative desorption of components of interest. Tenax GC has proved one of the most effective trapping mediums and has been widely used for the collection of volatile organic compounds from 'air', waters and complex matrices including biological materia1. 6 . 2
The sampling system described has been used successfully to study volatile material from diverse sources including • plant material, industrial furnaces, working environment atmospheres, and for ambient air monitoring. Extensive development of systems outlined in the literature has resulted in a versatile sample collection/elution system for routine use in the field or industrial workplace. An outline of a similar system is given by Versinos in which he describes the use of 2.5 g Tenax sample tube to record recovery checks on a series of standard compounds. The capacity of Tenax to adsorb and desorb a range of organic components was reported in detail by Brown and Purne11 9 , and Butler and Burke.'° • Practical details of the sampling and desorption system used by this laboratory are given, and an example of the collection and analysis of volatiles from a wood burning stove is used to illustrate the technique.
EXPERIMENTAL PROCEDURES Sample collection tubes consist of 170 mm lengths of glass lined stainless steel tubing 6 mm 0.D., 4 mm ID., previously baked at 500°C and packed with Tenax-GC ( 0.4 g) and held by silanised glass wool. New packing was pre-conditioned at 325°C for 25 hours in a stream of high purity nitrogen, and the sample collection tubes were re-conditioned at 300°C for 2 hours prior to use in the field. The tubes were held individually in stoppered glass containers, with a small amount of dried silica gel, for storage and transport to and from the sampling area.
Collection of the volatile organic components of the flue gas was accomplished by inserting the Tenax sample tube into a water cooled jacket (Figure 1) and drawing gases through the sample tube from the flue of the wood burning stove. The sample collection point was 4 m above the grate. A calibrated flow control valve was used to maintain the gas flow rate to the gas pump at 40 mL per minute for 2 hours.
Flow
Pump control valve
Figure 1. Sample Collection System.
Desorption of the collected volatile organic components was controlled by heating of the sample tube in a stream of carrier gas to "inject" the trapped components into the inlet of a gas chromatograph or gas chromato-graph/mass spectrometer system (GC/MS) for characterisation.
The heating block consisted of a 25 x 150 mm cylindrical stainless steel rod with two holes drilled longitudinally. The central hole accepts the stainless steel Tenax sample tube held in position by a 1/4' Swagelock fitting at one end, and a 1/16' Swagelock fitting for the carrier gas inlet at the other. The second drilled hole contained a thermocouple junction to monitor the temperature of the block. The heating element consisted of a single layer of No. 20 gauge B. and S. resistance wire of
1.779 Ohm/metre. The total length of wire wound over a sheet mica base was 7.2 m. A voltage of 50 V from a variable voltage transformer provided sufficient power to heat the block to 300°C in approximately 10 minutes. Figure 2 is a half scale drawing of the elution equipment.
The eluted organic components are carried by the gas stream to a length of 2 mm x 230 mm glass lined stainless steel tubing (C) bent to form a U shaped trap. Coupling of the sample collection tube to the U trap was accomplished using stainless steel Swagelock fittings silver soldered to the 2 mm tube and employing graphite ferrules to form a compression seal at the heating block end. At each end of the 2 mm tubing (points A and B) a brass lug was silver soldered onto the fitting to provide electrical contact. Fitting A consists of a Luer syringe needle coupling or, an additional length of glass lined tubing, for coupling directly to a capillary GC col urn n.
Immersion of the U shaped section of tubing into a liquid nitrogen bath condensed the organics eluted from the heated sample trap. A 10 minute time interval at the pre-selected elution temperature ensured efficient displacement of the organics from the Tenax. After removal of the liquid nitrogen bath, the 2 mm glass lined tubing was rapidly heated by the Passage of an electric current (40A from a welding transformer) between points A and B. The current was applied for 30 seconds and the maximum temperature reached was 300°C. The organics were vaporised and carried to the injector system of the GC or GC/MS. Resistance heating of the glass lined tubing at this current setting is sufficient to ensure that breakage of the tubing does not occur.
Figure 2. Sample Elution — Injection Apparatus.
'tater -jacket and Tenax Samole Tube
Clean Air/August, 1982 39
2188.6
80
11 J.
0 100 200 6.50
300 4'00 13.36
t 500
20.23 700
800
900 27.12
technique described could be accomplished on a routine basis using a number of sample tubes and despatching them to a central laboratory for analysis.
SUMMARY AND CONCLUSIONS An effective method for trapping volatile organic compounds from air and gas streams is presented. Construction details are provided and an example of the collection and an analysis of the flue volatiles from a wood burning stove is used to illustrate technique. Quantitative measurements of volatile components may be made by incorporation of a suitable bleed of a known concentration of a- specific component into the gas stream. Possible 0 applications of the technique include ambient air monitoring, forensic and customs search assistance, odour location and analysis.
Monitoring of volatile trace organic components in working and residential areas will become increasingly important as city populations increase. (There were 11 cities of over 1 million people in 1900, by the end of the century the number is expected to be over 500.) Trends in the lowering of ambient air quality and the health effects resulting need to be carefully documented at an early stage to avoid serious long term problems.
ACKNOWLEDGEMENTS The assistance of Mr. C. Richards in the construction of the equipment and the preliminary prototypes is gratefully acknowledged. The help of the staff and the use of the equipment of the Central Science Laboratory of the University of Tasmania is also acknowledged.
REFERENCES I. Giannovario, J. A., Grob, R. L., Rulon, P.
W., J. Chromatog. 121, 285, (1976). 2. Smith, R. G., Health Lab. Sc., 12, 167
(1975). 3. Rubinshtein, R. N. and Silchenko, S. A., ./.
Chromatog. 123, 251 (1976). 4. Pellizzari, E. D., Bunch, J. E., Berkley, R.
E., McRae, Anal. Chem., 48, 803 (1976). 5. Bellar, T. A., Lichtenberg, J. J., "The
Determination of Volatile Organic Compounds in Water by Gas Chromatography" EPA PubIn. EPA-670/4-74-009, Washington, DC (Nov. 1974).
6. Zlatkis, A., Lichenstein, H. A., Tishbec, A., Chromatographia, 6, 67 (1973).
7. Zlatkis, A., Bertsch, W., Lichenstein, H. A., Tishbec, A., Shunbo, F., Leibich, H. M., Coscia, A. M. Fleischer, N., Anal. Chem., 45, 763 (1913).
8. Versino, B., de Groot, M., Geiss, F., Chromatographia, 7, 302 (1974).
9. Brown, R. H., Purnell, C. J., J. Chromatog., 178, 79 (1979).
Table 1. Volatile Components from a Wood Burning Stove.
Component Boiling Scan
Point °C No.
I, 2-pentadiene 45 50 2, 3-pentadiene 48 55 acetone 56.5 57 hexane 70 63 benzene 80 74 2, 5-dimethylfuran 94 • 85 toluene 110 106 2-furyl methyl ketone 121 ethylbenzene 136 159 phenylacetylene 142 . 168 styrene 145-146 180 2-furaldehyde 162 218 benzaldehyde 179 236 dimethylphenol
(6 isomers) 210-225 247-248 p-methylbenzylalcohol 249 trimethylbenzene
(3 isomers) 164-170 253 benzofuran 173-175 287 naphthalene 217 573 azulene 270 574 dimethylbiphenyl
(5 isomers) 256-295 789 heptadecene 300 814 heptadecane 302 817
10. Butler, L. D., and Burke, M. F., J. Chromatog. Sc., 14, 117 (1976).
II. "Health Hazards of the Human Environment", W.H.O. Publn., Geneva, p.24 (1972).
12. "Hazards in the Chemical Laboratory", Muir, G. D., Ed., Chem. Soc. Publn., London (1977).
Table 2. Threshold Limit Values (TLV) for some Volatile Components
Component TLV (ppm) (mg/m 3 )
hexane 100 360 benzene 10 32 acetone 1000 2400 toluene 100 375 ethylbenzene 100 435 xylenes 100 435 furfural 5 20 - styrene 100 420 cresols 5 22
Table 3. Volatile Components of Boronia Headspace
Scan No. Identity
41
Carbon dioxide 80
Methylene chloride 01
Chloroform 10
Methylcyclopentane 23
Cyclohexane 40
Heptane 51
Methylcyclohexane 70
Toluene 200
Tetrachloroethylene 241
Xylene 293
Nonane 342
Monoterpene (unknown) 349
Isopropylbenzene 371 a-pmene 386
Camphene 392 ,3-pinene 400
Myrcene 416
Limonene 442
Linalool 522
Unknown 574
Menthone 600
Naphthalene 604
Ethylbenzene 705
Methylnaphthalene 736
Methyldecanoate 858
0-ionone 882
Dihydroactinidiolide
Figure 4. Total Ion Current Trace Boronia Volatiles Scan Number and Time.
100 -
1000 1100 Scan numbers
30.13 Time (minutes) .-
Clean Air/August, 1982 41
top related