Recycling of the water-phase

from hydrothermal conversion of biomass

Comparative study of water

composition using lignin and microalgae as feedstocks

Carlos Fellipe de Abreu Thomaka

Master thesis, 60 hp Master Program in Chemistry – 120 ECTS

2018-2019

I

Abstract

The transformation processes turn biomass into valuable products. They are

advantageous techniques that are necessary to reduce the use of fossil fuels and increase

the use of renewable resources. The hydrothermal carbonization (HTC) is a process that

requires great amount of water, biomass and energy to produce a material called

hydrochar. The hydrothermal carbonization also produces a liquid product, called

water-phase, that is usually neglected in most of the studies. In this project, the water-

phase from an HTC process using lignin and microalgae as feedstock were

characterized. Several analyses were performed to identify the composition, inorganics

concentration levels and properties such as pH. In addition to these analyses, the

recycling of the water-phase was performed to evaluate the impacts on hydrochar yield,

composition and inorganic concentration levels. The HTC process was conducted in

triplicates at 240 °C for 6 h in a 1 l reactor and recycled for four times. While the HTC

operation using microalgae was performed in triplicates at 240 °C for 6 h in 20 ml

reactors and recycled once due to lack of samples. In the first cycle the hydrochar yield

was 44.79 % and increased over four cycles to 50.98 %. The increase of the hydrochar

yield on the lignin process showed that the water-phase recycling is possible and

advantageous on the hydrochar yield perspective. The hydrochar yield of the

microalgae process also increased over the cycles (26.80 ± 6.22 %). The composition

identified mainly aromatic compounds such as guaiacol, vanillin and ethanone, 1-(3-

hydroxy-4-methoxyphenyl)- as the species with higher abundance in the analyzed

water-phases. The concentration of sodium and sulfur increased over the recycling from

8.75 to 22.91 g/l for sodium and from 2.14 to 5.06 g/l for sulfur. The increased

concentrations of these inorganics could represent a drawback on the recycling due to

their effects on the environment. The results are promising and numerous. They provide

new information about the compounds that can be found in the water-phase and the

possibility of reusing the water-phase to reduce costs in the process and consequently,

turning the HTC into a more profitable technique.

II

III

List of abbreviations

ALK Alkaline

DA Dealkaline

EPA Environmental Protection Agency

GC Gas Chromatography

HHV Higher heating value

HPLC High-Performance Liquid Chromatography

HTC Hydrothermal Carbonization.

LC Liquid Chromatography

MS Mass spectrometry

SCW Super Critical Water

STDev Standard Deviation

PAH Polyaromatic hydrocarbons

TOC Total Organic Carbon.

XPS X-Ray Photoelectron Spectroscopy

IV

Author contribution

The author conducted the laboratory experiments that included the hydrothermal

carbonization operation, gas chromatography analysis, solids analysis, ash content,

non-volatile residue, liquid-liquid extraction and pH measurements. The samples

generated by the author were also handled and pre-treated by him. The first 4 lignin

samples were provided by Alexandra Charlson, the data relative to these samples was

provided by Kenneth Latham. Microalgae sample were provided by Francesco (SLU).

The ICP-MS operation was conducted by Erik Björn at Umeå University. The student

had orientation on the ICP-OES by Erik Björn, and then the student conducted all the

analysis on this instrument. Andriy Rebryk assisted on the GC-MS analysis.

V

Table of contents

Abstract .......................................................................................................................... I List of abbreviations .................................................................................................... III Author contribution ...................................................................................................... IV Table of contents ........................................................................................................... V

1. Introduction ................................................................................................................ 1 Aim of the diploma work ........................................................................................... 1 1.1-Biomass ............................................................................................................... 1

1.1-Lignin............................................................................................................... 1 1.2-Microalgae ....................................................................................................... 2

1.2-Thermochemical processing ................................................................................ 3

1.3-Hydrothemal processing ...................................................................................... 4

1.4-A brief state of the literature: HTC of lignin and microalgae ............................. 5 1.5-Motivation and objectives ................................................................................... 7

2. Popular scientific summary including social and ethical aspects .............................. 8 2.1 Popular scientific summary.................................................................................. 8

2.2 Social and ethical aspects ..................................................................................... 9 3. Experimental ............................................................................................................ 10

3.1 Chemicals and samples ...................................................................................... 10 3.2 Analysis of provided samples ............................................................................ 11

3.2.1 pH, solid particles, ash content and non-volatile residues .......................... 11

3.2.2 GC-MS ........................................................................................................ 12 3.2.3 ICP-MS/OES............................................................................................... 13

3.3 HTC operation and water-phase generation ...................................................... 13

3.4 Analysis of generated samples ........................................................................... 14

3.5 Quality assurance and quality control for the GC-MS .................................... 15 4. Results ...................................................................................................................... 15

4.1 Analysis of provided lignin samples - pH measurements, solid particles, ash

content and non-volatile content .............................................................................. 15

4.1.1 pH measurements, solids, ash content and non-volatile residue ................. 15 4.1.2 GC-MS ........................................................................................................ 16 4.1.3 ICP-MS / ICP-OES ..................................................................................... 17

4.2 HTC operation –Hydrochar yield ...................................................................... 17 4.3 Analysis of generated samples ........................................................................... 18

4.3.1 pH measurement ......................................................................................... 18 4.3.2 GC-MS ........................................................................................................ 19 4.3.3 ICP-MS/ICP-OES ....................................................................................... 20

4.4 Microalgae recycling ......................................................................................... 21 5. Discussion ................................................................................................................ 21

5.1 Recycling results discussion – Hydrochar yield and composition change over

recycling ................................................................................................................... 22

5.2 Differences between the provided samples and generated samples .................. 22 5.3 Microalgae hydrochar yield discussion ............................................................. 23 5.4 Sodium and sulfur concentration ....................................................................... 24

6. Conclusions and Outlook ......................................................................................... 24 Acknowledgement ....................................................................................................... 25 References .................................................................................................................... 25 Appendix ...................................................................................................................... 31

VI

Appendix 1 – Instrumental Parameters and procedures .......................................... 31

Appendix 2 – False positive identified .................................................................... 32 Appendix 3 – Mismatches list.................................................................................. 36 Appendix 4 - GC-MS SPECTRA ............................................................................ 37

Appendix 5 – HTC operation full data sheet ........................................................... 85 Appendix 6 – Guaiacol Quantification Data set ...................................................... 86

VII

1

1. Introduction

The use of fast and natural growing materials as feedstock to provide energy and

valuable products is the main target of the green industry, which is necessary to help

develop a more sustainable world. Using fewer resources, such as water and biomass,

and generating fewer residues than the usual processes is an interesting option to the

evolution of industrial processes. Presently, the use of natural resources results in a

massive generation of waste. Due to a lack of knowledge about reusing resources in

industrial processes, water and biomass are currently not optimized. Hence, introducing

waste as feedstocks requires a remodeled process. Additionally, reducing the use of

water is a key factor to improving the sustainability of the green industry.

Aim of the diploma work

The studies aim is to obtain information about the composition of a hydrothermal

carbonization process that used lignin as feedstock; the impact of recycling the water-

phase in the hydrochar yield of a process using lignin as feedstock and a process using

microalgae as feedstock. The studies try to evaluate changes in the composition and

properties of the water-phase over the recycling cycles.

1.1-Biomass

Biomass can be defined as the amount of mass of a living organism 1 and “all the

living material in a given area: often refers to vegetation. Also called biota” 2. The

biomass has become important as an alternative source of energy and chemicals. The

most advantageous form of biomass is the lignocellulose 3. This material has an

estimated global growth of 146 billion tons per year and it is considered essential to the

sustainability of the planet 4. The attractiveness of this material grew constantly due to

its potential uses such as source of valuable products, food production, recycle pollutants

and remediate contaminated material 4–6. The lignocellulosic material’s fast growth

combined with its diverse applicability resulted in a vast generation of waste, which was

an important resource for the green industry that turned lignocellulose residues into

products. Among the many different sources of biomass, lignin and microalgae were the

focus of this thesis and they will be discussed below.

1.1-Lignin

The lignocellulosic material is mainly formed by three biopolymers: cellulose,

hemicellulose and lignin. Lignin is less used by the industry than the other two due to

the lack of knowledge on its use. However, it has been appearing more often in the

literature because of its potential, which will be discussed later 7,8. Lignin is the second

most abundant biopolymer and responsible for strengthening the lignocellulose

structure 7,9. This biopolymer requires more energy to break its structure than the other

two biopolymers 3,10. Moreover, the combustion of lignin generates more energy than

the other two biopolymers, it has a calorific value of around 23.3-26.6 MJ/kg, which is

3-4 MJ/kg higher than cellulose and hemicellulose 8,11–13. While lignin is composed of

three different monomers, cellulose and hemicellulose are composed of glucose

monomers.

Figure 1a shows the three different phenolic monomers with methoxy groups 10.

They are combined randomly into an amorphous and highly branched structure 14 to

form lignin. Their combination is still being studied, because the polymerization and

bonding depend on the material analyzed 3. Their aromatic nature also means that lignin

could be a source of aromatic compounds that have been mostly obtained by the

2

processing of fossil fuels 15. In addition Figure 1b shows flavor ester used in the industry

that can be obtained from the depolymerization of the lignin 16,17. This complexity of the

structure has been challenging in the endeavor to find a more profitable use for the lignin

rich waste generated in the pulp/paper mill industry.

Figure 1 - a) Lignin monomers; b) Guaiacol and vanillin are important to obtain flavor esters. Adapted from 10.

The pulp and paper industry is one of the major industries in the world, with an

estimated world production of 390 million tons 18,19. It has an important role in many

countries, including Sweden, representing a large part of the economy. During the

processing of the pulp/paper industry, the lignocellulosic material undergoes physical

and chemical treatment to dismantle the structure and separate the biopolymers 20. One

of the most commonly adopted chemical treatments has been Kraft pulping, which uses

powerful chemicals, such as sodium sulfide (NaS) and sodium hydroxide (NaOH) 21,22.

Kraft pulping results in an environmentally toxic waste, called black liquor, that

contains mainly lignin and hemicellulose 23. Black liquor was often used in recovery

boilers to optimize the energy usage, e.g., a Swedish kraft pulp mill generates an energy

excess of around 7 GJ/m³ton for pulp produced 24. As mentioned above, the combustion

of lignin generates around 24 MJ/kg. Therefore, the removal of lignin from the black

liquor reduces the excess of energy generated in the recovery boilers 24. It was estimated

that only 2 % of the lignin obtained from the pulp/paper waste was given any application

besides energy generation in recovery boilers 8. Lignin extraction from black liquor can

be made by acidification, with sulfuric acid, lignin precipitation and filtration 25,26. Kraft

lignin contains sulfur and sodium, around 18.1 % of sodium concentration in total

dissolved solids 27.The need of studying the transformation of lignin is essential to

recover valuable materials and reduce waste emissions. As mentioned above, biomass

can be from different sources. The microalgae are a source of biomass that can be

cultivated in wastewater. It has a waste emission mitigation capacity that will be

discussed further.

1.2-Microalgae

The microalgae have been appearing in the literature as another advantageous

form of biomass. It uses waste water and additionally carbon dioxide that is bubbled in

the water as source for carbon and nutrients for growing 6.The microalgae is an

unicellular organism that reproduces with a faster rate than terrestrial plants and it is

composed by a mix of lipids, carbohydrates and proteins 28–30. In the literature, it is

3

possible to find different applications for this type of biomass such as: production of

acetic acid, biofuel and nutritional supplements 31–34. The microalgae ability to fixate

CO2 combined with its fast-growing cycle turns it into an attractive material for

environmental science and sustainability 30.

Currently, high quantities of CO2 (around 7 % of the global emissions) are

generated by the cement industry. The intensive need of energy to maintain the furnaces

working and burning emissions are responsible for the high generation of carbon

dioxide 35. Which turns this industry into a potential candidate to use microalgae to

reduce the amount of released CO2 6,36.

The algal biomass cultivation dispenses the need of arable land and clean

water 37,38. Natural microalgae production is low and costly 39. The exploitation of flue

gas in combination with wastewater has the potential to make the microalgae production

more attractive 39.

Hence, after determining the source of the biomass, it is necessary to choose a

transformation process. The transformation of biomass into useful products such a soil

amendment, fuel or adsorbent material. Most of the transformation processes requires

low moisture in the feedstock. Since the microalgae is cultivated in an aquatic

environment, the high-water content of the microalgae leads to a need of pretreatment

in most of the transformation processes 40, which represents disadvantages of this type

of biomass. Nonetheless, the green process should be stimulated, and hindrances needs

to be studied and bypassed. Thermochemical processing is an alternative to treat biomass

and it is widely used for its transformation into useful and valuable products 13. It

transforms biomass into products from biofuels (gas, liquid and solid) to adsorbent

material for remediating processes 5. Some thermochemical processes will be covered

in the next section.

1.2-Thermochemical processing

The thermochemical processing is the oldest way handling biomass since a

simple bonfire is an example of it 13. It is based on applying heat to the biomass to obtain

products or energy 13. Many different types of thermochemical processes exist, and their

conditions will be further explained in the following sections. The thermochemical

biomass conversation processes are flexible in terms of conditions such as the

parameters of temperature and pressure; environment such as inert or oxidative; final

products such as gas, liquid or solid; and pre-treatment requirement or not 13. Figure 2

illustrates a simplified diagram including the most common thermochemical processes

available in the literature. The drying step is the major source of cost and time of the

pre-treatments 40,41. Therefore, a separation can be made into processes that require

drying and processes that can be conducted without this pre-treatment of the biomass

such as hydrothermal processing. Pyrolysis, combustion and gasification are shortly

explained below.

Figure 2 - Thermochemical processing types, biomass conversion with and without pretreatment. Adapted from 13.

4

Pyrolysis is an important biomass conversion technology that is usually used to

maximize the amount of liquid fuel produced, called bio-oil, is attractive in terms of

logistics 42. However, it is possible to alter the temperature and reaction time to obtain

gas and solid products 43.This technique uses a different range of temperatures in an inert

environment, absence of oxygen 40. The reaction time may vary from seconds to days,

while the used temperatures can vary from 290-1000 °C, requiring variable heating

rates 40. Moreover, the requirement of pre-treatment such as fragmentation and drying

of the biomass can generate additional costs 40.

Combustion is the total oxidation of the biomass 44. This thermochemical process

is a technique that basically converts all biomass into energy 42. It uses high

temperatures, up to 1000 °C, and usually requires fragmentation and drying of the

biomass 45. Nonetheless, the process has low energy conversion efficiency 46. While the

combustion can generate, depending on the conditions and feedstock, large amounts of

pollutants such as CO2, inorganic volatiles (potassium, sulfur and nitrogen) and even

polyaromatic hydrocarbons (PAH). The PAH are well-known toxic compounds that are

constantly monitored 45, and they are issues associated with this technique.

The gasification is an efficient biomass conversion technology that uses high

temperature and partial oxidizing environment 47. Although the process is considered

efficient for transforming biomass into energy, it requires different pre-treatments and

catalyst 46,48. The pre-treatments of the feedstock used in the gasification are size

fragmentation, densification, and drying 46,48. Therefore, the gasification is not simple

and demands a complex set-up.

Evans et al. 2010 conducted a sustainability assessment that evaluated the use of

pyrolysis, combustion and gasification for biomass conversion to generate electricity.

After analyzing factors such as greenhouse gas emissions, electricity price and

efficiency, the authors concluded that processing biomass with these thermochemical

processes were favorable when comparing to other energy generation options such as

use of fossil fuels. Furthermore, the authors included the negative impacts of using

agricultural crops that could be used as food and the excess of water used in the

processes 44.

Drying is one of the most common pre-treatments required for conventional

thermochemical processes, as illustrated in Figure 2, in contrast to hydrothermal

treatment techniques which can use wet biomass as feedstock. The hydrothermal

treatment is a technique that has existed for a long time, but its importance has been

rising within the last few years due to its applicability and flexibility. The hydrothermal

treatment does not require drying the biomass; it can use mild temperatures (lower than

300°C); and it can produce liquid, gas or solid products 13. The hydrothermal treatments

will be explained in the next section.

1.3-Hydrothemal processing

Hydrothermal processing is roughly 100 years old 49. The processes use water as

a reaction media, which represents a way to transform biomass into products and deal

with usual hindrances such as pre-treatment of feedstock 41,50.

The water can be used in its supercritical or subcritical conditions, which are

state related to the critical point. The critical point is the highest temperature and

pressure, represented on a phase diagram, where liquid and gas phase can coincide 51.

The water has a critical point of around 374 °C and 22.1 MPa 52. Therefore, supercritical

conditions are characterized by the temperature and pressure above the critical point,

while subcritical conditions are any temperatures lower than the critical point 51.

Supercritical and subcritical conditions are commonly used in the industry to alter the

properties of solvents and each state has its own effects on the solvent properties such

as: dielectric constant, viscosity and solubility. While the water is a well-known polar

5

solvent, it is possible obtaining non-polar characteristics when using different

conditions 53.

There are three types of hydrothermal processing: hydrothermal carbonization

(HTC), hydrothermal liquefaction (HTL) and hydrothermal gasification. The HTC uses

subcritical water as a reaction media while the other two techniques make use of

supercritical water for the process.

The hydrothermal liquefaction produces mainly liquid products, with solids and

gases as byproducts. It uses temperatures from 250-373 °C 54. It is a process with lower

temperatures than pyrolysis and no need for pre-treatment of biomass 54. The

hydrothermal gasification uses temperatures around 600°C and pressures around

30 MPa, much lower than the normal gasification 800-1000 °C 55. Hydrothermal

liquefaction and gasification are not the focus of this project and will not be discussed

in detail.

Hydrothermal carbonization, also known as wet torrefaction, is a process that

maximizes the solid fraction in the products. Therefore, the process still generates a

liquid phase and small amounts of gases, between 1-3 % of the raw material 56. The solid

product obtained in the HTC is called hydrochar. The hydrochar is generated under wet

conditions, which results in a mixture of solid and liquid product, i.e. a slurry. A

separation process, usually filtration, must be used to separate the hydrochar from the

liquid. The liquid product obtained from the separation is referred to as process water or

water-phase.

The HTC process uses a huge amount of water. The biomass/water ratio can vary

from three to ten times 57. Once the process gets scaled up, the water usage will be a

financial and environmental issue. The process water from the reactor contains species

which need treatment prior to the release in the environment. Since the focus of the HTC

process research is with the solid product, the liquid has been neglected in most of the

recent literature 5,34,37,38,58–63. However, few studies have shown that the recycling of the

water-phase can increases in the hydrochar yield 57,64–66. One of the gaps of the literature

is the lack of a study containing information about the recycling of the water-phase

generated in a process with microalgae and studied with the composition of the water-

phase during the recycling with lignin as feedstock. Another gap is the lack of

knowledge of the water-phase composition of an HTC using lignin as feedstock. This

study seeks to obtain data which will help to address the research gaps. Therefore, a

short review on the literature will be presented in the next section.

1.4-A brief state of the literature: HTC of lignin and microalgae

The literature research provided information of the current state of the

hydrothermal carbonization. Table 1 represents the literature summarized on HTC of

lignin and microalgae, including recycling of the water-phase. The literature that

contained lignin and microalgae used as feedstock was briefly described below.

In Kang et al. 2012, dealkali lignin was used in an HTC process at 225 °C,

245 °C and 265 °C for 20 hours. The study presented hydrochar yield, energy recovery,

carbon recovery and higher heating value (HHV) of the hydrochar produced. The

authors determined that higher process temperatures accelerate the process generating

lower yield and higher carbon content.

In Atta-Obeng et al. 2017, lignin from a biorefinery was used to produce

hydrochar in an HTC process. This study used different process temperatures to analyze

the effect on the hydrochar yield morphological and physicochemical properties of the

hydrochar obtained. The authors identified the highest yield on the lowest process

temperature (200°C) and major morphological changes occurred in processes higher

than 300°C.

6

In Wikberg et al. 2016, kraft lignin acidified and alkalinized were used in an

HTC process at 220 °C for 4 hours. Their study analyzed kraft lignin and the hydrochar

composition using pyrolysis/gas chromatography. The authors identified that the kraft

lignin was able to produce higher yield of hydrochar and higher carbon recovery than

glucose and galactoglucomannan. The acidic and alkaline hydrochar presented similar

compositions with a visible higher presence of guaiacol and p-cresol.

Table 1 - Gathering of the literature on HTC, recycling and HTC of microalgae

Study Feedstock Reference

HTC

Recycling

Poplar wood chips 64Stemann 2013

Grape pomace, orange pomace, poultry litter 66Catalkopru 2017

unbleached tissue paper 65Weiner 2014

loblolly pine 57Uddin 2014

HTC of

Lignin / No

Recycling

Kraft Pulp, Kraft lignin acidic, kraft lignin alkaline 61Wikberg 2016

lignin commercial 62Atta-obeng 2017

Lignin (DA) 58Kang 2012

cellulose, xylan, lignin 67Kim 2016

HTC

microalgae

Chlamydomonas reinhardtii, lignocellulosic prairie grass (20%) lignin, D.

salina

37Steven M. Heilmann

2010

Dunaliella salina, Chlamydomonas reinhardtii 38Steven M. Heilmann

2011

Spirulina, loblolly pine, sugarcane bagasse, Lipid extracted algae spirulina 32Broch

Nannochloropsis sp 33Lu 2015

A. platensis 68Yao 2016

Hippeastrum. reticulatum, Chlorella vulgaris 34Park 2018

In Kim et al. 2016, lignin was used in an HTC process in different temperatures

(180-280 °C) for 30 min in a 1 L reactor. The authors determined that the decomposition

of the lignin initiated at 250 °C and that the process temperature of 200 °C was optimal.

However, the carbon fixation did not increase until the reaction at 250 °C.

The information gathered about HTC processes using lignin was that lower

temperatures presented higher hydrochar yield. Also, no study showed the composition

analysis of the water-phase generated.

In Heilmann et al. 2010 and Heilmann et al. 2011, microalgae were used in an

HTC process to generate hydrochar. The authors presented a series of analysis of

different algal materials and the hydrochar formed along with comparation between the

lignocellulosic materials and hydrochar. The authors also identified the future

importance of evaluating the liquid product of the process due to the high nitrogen

content.

In Lu et al. 2015, microalgae were used in an HTC process to facilitate the

extraction of lipids for biofuels and dietary supplementary purposes. The authors

identified that the HTC process produced a hydrochar that retained around 85 % of the

total fatty acids.

In Broch et al. 2014, microalgae were used in an HTC process at 175-215 °C for

30 minutes in a 2 L reactor. The authors determined high-value chemicals in a low

amount (less than 1 % of the dry algae). However, the authors determined that the

microalgae were able to produce an energy-dense hydrochar.

In Yao et al. 2016, microalgae were used in an HTC process to be used along

with algal production. The authors recovered the water-phase generated and used for

another algal production. The authors also determined that the method could save up to

60 % of the conventional nitrogen usage.

7

In Park et al. 2018, microalgae were used in an HTC process at 180-270 °C for

60 minutes. The authors evaluated carbon recovery, carbon content and energy recovery

of the hydrochar obtained. They determined that the microalgae were an efficient source

to generate a potential biofuel.

The gathering of the studies gives information about the process temperature and

time. The HTC can use microalgae as a feedstock to obtain a hydrochar with an efficient

carbon fixation and that can be used as a biofuel. Also, the gathering presented no studies

about the recycling of the water-phase on the HTC.

1.5-Motivation and objectives

As mentioned above, the HTC process can transform residues that contain

biomass into valuable products using mild temperatures and water as solvent. One of the

disadvantages of the process was the amount of water required, that can vary from seven

to ten times the amount necessary. This led to a need to reduce the water consume from

the environmental and social aspects. The water-phase is usually ignored during the

studies with lignin. The lack of knowledge of the water-phase composition of an HTC

process using lignin is evident. Therefore, it was necessary to investigate the

composition of the water-phase and the possibility of reusing the water-phase without

reducing the hydrochar yield. Also, it is important to understand that the recycling may

increase the yield of the hydrochar or concentrate toxic compounds in the water-phase.

The inorganics are commonly present in the water-phase such as sodium and sulfur.

The inorganics present in the biomass are also of importance due to impacts in

the environment. The sodium is considered as hazardous in groundwater and often

undetermined according to the environmental protection agency (EPA) 69. The salinity

of irrigation water can be harmful for the crops and may be considered toxic to sensitive

crop, i.e. fruit trees 70. While elemental sulfur and sulfur species have harmful effect on

terrestrial animals, humans, aquatic environmental 69,71–73. Also, sulfur is common to be

the cause of corrosion problem 74.

It is known that the HTC can “clean” the biomass, while the water-phase

generated contains most of the inorganics present 75. Moreover, the lignin obtained from

the black liquor contain contaminants such as sulfur and sodium ( around 18.1 % 27).

The water-phase containing those inorganic cannot be discharged in the water sources

without treatment 27. Hence, the analysis techniques and methods about the water-phase

generated should be enough to give information about the concentration levels of

inorganics, composition and acidity.

The water-phase generated in HTC processes is typically studied by analysis of

pH, total organic carbon and a composition analysis such as gas chromatography with

mass spectrometry (GC-MS), liquid chromatography with mass spectrometry (LC-MS)

or inductively coupled plasma with mass spectrometry (ICP-MS) 57,64–66. The glucose

reactions in the HTC and water-phase composition are well-known and abundant in the

literature 3,76. Nevertheless, the literature that utilized these techniques did not used the

lignin as feedstock. The information about lignin composition were searched for

different processes and studies 77–80.

The species present and how the composition changes over the recycling can be

identified with a non-target analysis of this water-phase. The literature gathering, gave

enough information to understand the composition of lignin and what to expect on its

water-phase. Since lignin is based on three different phenolic monomers, a mix of

phenolics and methoxylated molecules were expected and, some of them, constitutes a

good variety of antioxidants 49. Therefore, the gas-chromatography with mass

spectrometry was selected for the non-target analysis. This method uses a library tool

that facilitates the determination of unknown species.

8

Vanillin, catechol and syringol are usually found in the water-phase of a

hydrothermal decomposition of lignin 61,81,82. The vanillin can be used to produce

vanillic acid. This can be used as a flavoring agent, while the catechol is widely used as

a precursor in the industry to synthetize chemicals such as pesticides and

pharmaceuticals. The syringol can be used to produce syringic acid, which presents

useful biomedical properties and great importance in the industry 49,83. Hence, the

presence of those compounds can attract more attention to the water-phase generated.

Although, lignin and microalgae have distinct composition the microalgae were another

important focus of this project due to its benefits discussed earlier.

The microalgae were provided by the Francesco of the Swedish university of

agricultural studies sciences (SLU). According to the literature, it is possible to obtain

cellulose and starch in the microalgae composition 84. Starch and cellulose are sugar

based biopolymers which are decomposed into glucose during the thermal treatment and

it generates a series of different organic molecules such as organic acids and aldehydes76.

Also, it is commonly found HTC processes that used microalgae as

feedstock 32,34,37,38,68,85. It was not possible to find literature that studied the recycling

and the water-phase composition of the water-phase on an HTC process using lignin.

Therefore, analyzing the water-phase and obtaining more information of its composition

and evaluating the effects on the hydrochar yield is of great importance.

2. Popular scientific summary including social and ethical

aspects

2.1 Popular scientific summary

Biomass is a renewable abundant natural resource that can be used in many

industrial activities. The used biomass is usually a plant-based material composed of

different molecules. The most known molecules are cellulose, hemicellulose and lignin,

where lignin is the most complex molecule of them. Its structure changes for every

source of biomass. Another source of biomass that is being studied more by the research

community is the microalgae. This organism grows faster than the terrestrial plants and

it is produces in an aquatic environment.

The processes that changes the biomass into useful products are transformation

processes. These processes make use of biological activities or temperature, where

temperature is a key factor in thermochemical processes. The presence of water in the

biomass is counterproductive due to the need of more energy to break the material’s

structure. The hydrothermal processing uses temperature and water to transform biomass

into products. The use of water is beneficial in this process and a wet biomass can be

used without previously drying. Currently, there are three different types of

hydrothermal processing: hydrothermal carbonization (HTC), hydrothermal

liquefaction (HTL) and hydrothermal gasification. The hydrothermal carbonization

demands lower temperatures of the hydrothermal processes. Also, it produces mainly

solids and liquid products.

The project sought information about the liquid product composition of a lignin

HTC, the recycling of the liquid products into the process, and the liquid product

composition of a microalgae HTC. Furthermore, the composition was studied during the

recycling cycles and the impacts on the solid product yield.

As a result, compounds in the liquid product were identified which could be

alternatively used by the industry. Those compounds are usually obtained from different

non-renewable sources. The recycling of the liquid products did not show an increase or

decrease in the solid product yield. However, this information was valuable to allow the

water recycling and to avoid excessive use of water.

9

2.2 Social and ethical aspects

The global risk report from the world economic forum 2018 classifies water

crises as being number five on the top ten risks in terms of impact 86, while failure of

climate-change mitigation and adaption is number five on the top ten risks in terms of

likelihood 86. However, climate change has an impact on the water supply 87.

Industrial processes have a major impact on the environment. The pulp/paper

mill is the third largest industry to use freshwater in its processes and, consequently,

produces as much wastewater as it uses water for their activities 88,89.

This work was aimed to provide information of a green process used to transform

waste into useful products, to reduce the use of resources and to obtain information about

the products that can be generated.

The demand of clean water resources increases together with the population.

Most of the industrial activities demand a considerable amount of water volume for

cooling or a transformation process. The reuse of the water in a transformation process

can be essential to make it feasible. In addition, reducing the amount of water for

industrial processes could reduce the environmental impact on the planet.

Another environmental impact in industrial activities is the generation of great

amounts of waste. Great water demand and generation of waste are characteristics of the

pulp/paper industry. The pulp/paper mill waste contains a substance called lignin, which

is present in the composition of the plants. The lignin is a high-energetic molecule that

can be burned to produce energy. This complex molecule can be used in transformation

processes to obtain a versatile material, called hydrochar. The hydrochar can then be

used as a fuel, adsorbent material or soil amendment.

Hence, to reduce the impacts of the industrial activities using natural resources

wisely is a key factor. Another important resource that has been highlighted in the

research community is the microalgae. However, microalgae cultivation is costly due to

the need of nutrients in the media. The use of wastewater generated in industry could

reduce these costs, since the wastewater already contains some of the needed nutrients.

In addition, microalgae are also able to mitigate global warming. The use of microalgae

is associated with the remediation of wastewater ponds, due to CO2 fixation and

absorption of contaminants such as ammonia 90.Furthermore, the reuse of lignin to

obtain fuels or valuable materials is associated with the reduction of CO2 (greenhouse

gas) emission due to reducing the use of fossil fuels, which generate greater amount of

greenhouse gases91.The most worrying impacts of industrial activities are the generation

of waste and the use of large quantities of water. The pulp/paper industry plays an

important role in the impacts mentioned. The pulping is the first stage of the paper

production industrial process 18. The bleaching of pulp generates compounds that can be

found in the decomposition of lignin such as guaiacols, syringols and catechols 88,92. The

kraft pulping is the chemical process that is widely used. This technique uses sodium

hydroxide and sodium sulphite and generates around 50 m3 of effluent per ton of paper 93. The effluent contains around 11-25 g/l of lignin 93.

Another listed industry that plays a major role in environmental impacts, is the

cement industry. The cement industry is responsible for around 5 % of the global CO2

release 6. This discharge is associated with the demand of the energy to keep the furnaces

working and to obtain the products of the calcination of the raw materials 35. The

cultivation of microalgae on wastewater contaminated with flue gas from the cement

industry is feasible and synergetic with needs to further reduce the CO2 emission 6,36.

The HTC process can turn this cultivated biomass into biofuel that can then be used in

the same industry, closing a loop and reducing the need of fossil fuels to generate

electricity.

The foment of the green processes is advantageous for the environment and

synergetic for some of the pulp/paper mills and the cement industry. It is undeniable that

the world is at the risk due to pollution, greenhouse effect and water scarcity. Improving

10

the HTC process, reducing its water consumption and improving its yield will be

essential to increase its use among the industry.

3. Experimental

The experimental part was divided into three segments: (i) analysis of the

provided lignin and microalgae samples, (ii) HTC operation and water-phase generation

and (iii) analysis of generated samples.

3.1 Chemicals and samples

The chemicals used were phenanthrene D10 (Sigma Aldrich), guaiacol (Sigma

Aldrich), p-cresol (Sigma Aldrich), dichloromethane (Fisher Scientific), nitric acid 65 %

(Suprapur), acetone (GPR Rectapur), sodium sulfate (Merck), dealkaline lignin (TCI

Chemicals), sulfur standard for ICP-MS (Spectrascan). Water-phase samples from HTC

lignin processes were provided to the author for an initial study. Table 2 compiles

information about the origin of the samples. The provided samples were DA-280-12,

DA-300-12, ALK-300-12 and ALK 280-4, while the generated samples were 1L0-4L4

and microalgae.

Table 2 - HTC Sample information: feedstock used, temperature of the process and process time

Sample Name Feedstock Temperature (°C) Time (h)

DA-280-12 Dealkaline lignin 280 12

DA-300-12 Dealkaline lignin 300 12

ALK-300-12 Dealkaline lignin (with alkaline treatment) 300 12

ALK-280-4 Dealkaline lignin (with alkaline treatment) 280 4

1L0-1L4 Dealkaline lignin 240 6

2L0-2L3 Dealkaline lignin 240 6

3L0-3L4 Dealkaline lignin 240 6

4L0-4L4 Dealkaline lignin 240 6

Microalgae Microalgae 240 6

The lignin hydrochar samples (n=4) were obtained during carbonization of 100 g

of lignin and 700 ml of deionized water in a 1000 ml HTC reactor. X-ray photoelectron

spectrometry (XPS) data was provided with carbon content in biomass and in the

hydrochar.

The XPS data analysis from the DA-280-12 was used to obtain an estimative of

the carbon content that can be found in the water-phase. The XPS data provided

information about the atomic carbon percentage content on the surface of the feedstock

and the hydrochar generated. Therefore, a balance calculation was carried out to estimate

the amount of carbon on the water-phase.

The samples were generated in an HTC reactor of 1000 ml in 240 °C during 6 h.

The samples were named in a way of identifying the week produced and the number of

the cycle. The weeks were 1-4 and the cycle were from 0-4. The cycle zero is the first

run with pure deionized water and the run number four is the last recycle. Therefore, the

experiment is characterized by four recycles for each week. However, the sample 2L4,

which corresponds to the second week fourth run could not be collected due to an error

in the procedure. The reactor dried out completely, there was some leakage during the

process and no liquid could be collected.

The analysis conducted on each sample were slightly different. The water-phase

samples DA-280-12, DA-300-12, ALK-300-12 and ALK-280-4 were to evaluate the

analysis and their importance. It was necessary to gain knowledge to understand the

11

samples and the relevance of the analysis. Table 3 provides information about the

analysis conducted on each of the samples. The pH analysis was conducted on all

samples except the microalgae, since there was not enough water-phase (pH meter;

Mettler Toledo seven easy). The non-volatile residue analysis (NVR) was used only on

the samples DA-280/300-12 and ALK-280/300-4/12. The GC-MS was utilized to

identify the organic compounds on the sample DA-280-12, microalgae and generated

samples (1L0-4L4). While the ICP-MS and inductively coupled plasma with optical

emission spectroscopy (ICP-OES) were used to quantify the amount of sulfur (S) and

sodium (Na), respectively. Table 3 - Overview of the analysis conducted on the samples.

Analysis Sample

Name

pH Solids

particles

Ash

content

Non-volatile

Residues

GC-

MS

ICP-MS

and ICP-

OES

Samples produced

by the author in

the HTC

DA-280-12 X X X X X X -

DA-300-12 X X X X - X -

ALK-300-

12

X

X X X - - -

ALK-280-4 X X X X - - -

Microalgae

-

- - - X - X

1L0-4L4 X - - - X X X

All experiments were conducted in triplicates and a quality blank was produced

to determined quality of the results. Means and standard deviations (STDev) were

calculated for the samples 1L0-4L4. The samples 1L0, 2L0, 3L0 and 4L0 were used to

obtain the mean run 0. The sample procedure was then adopted for the run 1, run 2, and

run 3.

3.2 Analysis of provided samples

3.2.1 pH, solid particles, ash content and non-volatile residues

The samples were removed altogether from the freezer and placed in the fume

hood during the analysis period. The pH measurements were conducted on the next day,

after defrosting, and it was intended to be repeated every week for four weeks to verify

the stability. However, only the sample DA-280-12 could be measured in two different

weeks due to equipment issues that followed this analysis. Therefore, the samples DA-

300-12, ALK-300-12 and ALK-280-4 could only be measured in the first week. The

solid analysis was conducted using paper filters with different pores sizes 10 μm

(Munktell Ahlstrom Grade 3 125 mm) and 0.45 μm (Supelco nylon 66

membranes 47 mm). Figure 3 illustrates the partitioning of the water-phase and

facilitates an overview of the different particle sizes distributed in the samples.

First, 5 ml of the water-phase using a glass pipette was transferred directly to the

first pre-dried paper filter (10 μm), dried in an oven 110 °C overnight. Then 5 ml of

distillated water was used to wash the filter afterwards to make sure that the smaller

particles would be collected in the end. The volume was collected in a small beaker,

5 ml of distillated water was used to clean the Buchner flask. The paper filter was then

changed to the 0.45 μm and the solution was filtered again, with 5 ml of distillated water.

12

The paper filters were cautiously collected and set to dry in an oven at 110 °C overnight.

The ash content was measured after placing the filter paper inside crucibles and burning

in a furnace that was set to ramp the temperature 600 °C in 4 h and hold the 600 °C for

2 h to assure that all the material is burned.

Figure 3 - solid partitioning

The non-volatile residue analysis was conducted by measuring 10 ml and 5 ml

of each sample. Therefore, the sample was put into a crucible and dried in the oven

(50 °C) for two days to ensure that all liquid evaporated. The remaining content was

called non-volatile residue. The results were presented in percentage, which was

calculated using Equation 1.

Eq 1

3.2.2 GC-MS

The gas chromatography with mass spectrometry (GC-MS) is a technique that

separates and identify many compounds in a mixture. The sample is injected through a

column with determined affinity to polar or non-polar compounds 94. Whereas the

sample is vaporized, a carrier gas (helium) is used to transfer the species through the

column 94. The compounds travel throughout the column at different retention times due

to their molecular size and polarity of the molecule. At the end of the column, the

compounds reach the mass spectrometer where they are bombarded by electrons 94. The

fragmentation of the compounds is measured and compared to a library to identify the

compounds 94.

The GC-MS was selected due to its ability to identify compounds with facility

with the use of a library software (Agilent technologies, MassHunter Workstation

quantitative analysis version B.08.00/Build 8.0.598.0). The technique required samples

without any solids and water content. The preparation of the samples included dilution

1:10, a liquid-liquid extraction followed by a filtration in syringes. The procedure is

more detailed in the Appendix 1.

Peak identification was accomplished by comparing mass spectra to the mass

spectral library of National Institute of Standards and Technology (NIST) 2017. In order

to make the results comparable, a surrogate standard (phenanthrene D10) was used to

estimate the efficiency of the step prior to the chromatography (filtering and liquid-

liquid extraction). The calculation of the surrogate standard recovery was based on 95. It

was a simple ratio between the component peak area obtained in the samples that were

filtered and extracted and the component peak area a sample with known quantity of

surrogate standard in DCM. The surrogate standard was not chemically similar to the

targeted samples. Moreover, matrices effects could not be assessed. The use of an

internal standard was necessary but could not be completed due to the lack of resources.

The base peak area and component area were the parameters used for analysis. The base

peak area is the area of the highest intensity peak identified for a certain species. While

the component area takes all the peaks related to the species identified.

𝑁𝑉𝑅 % =𝑁𝑉𝑅(𝑔)

𝐿𝑖𝑞𝑢𝑖𝑑(𝑔)∗ 100

13

3.2.3 ICP-MS/OES

This technique dissociates the species into atoms prior to analysis. Therefore,

only elemental analysis is possible. The sample as liquid droplet was injected, sprayed

and mixed to an ionized gas, called plasma 96. The mixture is called aerosol and the

plasma is a state of the matter with distinct properties for the solid, liquid and gas

phases 97. It possesses great energy and it dissociates the atoms of the molecular species

and ionizes them, further 96. The element ion formed on the ICP is then transferred to

the mass spectrometry to be measured and identified 96. This analysis is considered to

have a low detection limit for the elements that range from less than 0.10 ppt to

10.00 ppb 96. Sodium is abundant in greater quantities and it cannot be quantified

without great dilution. The subsequent technique, ICP-OES, was able to quantify the

sodium amount without further dilution. The ion formation follows the same procedure.

The difference lies in the detection method. The elemental ions formed are excited into

a “higher” state 96. When the electrons drop from this state, they emit a photon. This

photon is then redirected by mirrors and measured and later identified and quantified 96.

The induced coupled plasma analysis was selected due to facilitate determination

of inorganic concentrations of water samples. Initially, the ICP-MS (Perkin Elmer

SCIEX / Elan DRC-e Axial field technology) and ICP-OES (Perkin Elmer Optima

2000DV) analysis were conducted for the samples DA-280-12 and DA-300-12.

The XPS data obtained from the previous samples allowed the estimation of

sulfur and sodium quantities. The samples were filtrated in 0.45µm syringe filters and

diluted with a factor of 1000 to set the values closer to the detection limit values of the

equipment.

The sulfur was detected in ICP-MS equipment using oxygen as a reaction gas,

to reduce interferences. The sulfur species are highly reactive with the oxygen reaction

gas and forming another species (SO). Consequently, the SO species were measured

instead of the S. The sodium was detected in the ICP-OES equipment due to the

detection limits of the equipment. A set of standard solutions were prepared in the range

of 1-20 mg/l and acidified with 2 %v/v of 65 % HNO3 (Suprapur). The sulfur solution

(Spectrascan) 1001 ± 3 µg/ml was used to prepare the standards, while a sodium sulfate

solution (Merck) of 1 mg/ml was prepared in the lab and used to prepare the standards.

3.3 HTC operation and water-phase generation

The HTC equipment was set to run at 240 °C and to hold this temperature for 6 h

and then cooled down to a temperature around 30 °C. No heating curves were obtained,

but after 1 h the target temperature was reached. The water-phase produced on the first

run was identified as 1L0, while the first recycle was 1L1 and then successively. The

water-phase was recycled for four-times for each replicate. Figure 4 illustrates the

process, where the make-up water was the volume necessary to set the volume back to

700 ml. The cleaning operation was conducted as fast as possible to reduce the time that

the water-phase rested outside, and the volume of the sample analysis was 50 ml. The

stirring part of the reactor was not used, and the cooling coil was located around the

stirring part of the reactor.

14

Figure 4 - Schematics of HTC process and recycling

The calculation of the hydrochar yield was based on the loaded biomass amount,

lignin and microalgae, respectively. The yields were calculated using Equation 2.

Eq 2

A triplicate experiment with one recycling cycle of a microalgae HTC

experiment was conducted. The microalgae experiment was conducted in an HTC

process in 240 °C and 6 h in 20 ml reactors due to scarcity of the precursor. The

microalgae mass was weighted 10 g and 8 ml of deionized water was used for each

reactor. The microalgae sample had around 15 % of dry mass. The small reactors leaked

during the experiments, turning into an inconvenience to the repetition of the

experiments. Since, not much volume was recovered, the pH analysis was not

conducted. The GC-MS experiments were conducted similarly to the lignin samples. A

method developed by the student was used to estimate the amount of non-reacted lignin

and to calculate the yield of hydrochar. The method was consisted in weighting

around 1.0 g of the mass obtained from the HTC and washing with acetone until a clear

coloration was obtained.

3.4 Analysis of generated samples

The analysis of GC-MS and ICP-MS/OES for the generated samples were

conducted the same way as the provided samples. While the pH analysis was performed

rapidly after defrosting of the samples in a room temperature water bath to avoid any

possible decomposition that may occur. There was no analysis of solids, ash content and

non-volatile residues for the generated samples. The generated samples were used to

attempt the quantification of phenol, 2-methoxy-(guaiacol).

To quantify a certain species a calibration curve covering the estimated

concentration range is necessary. However, no information about the concentration

levels of guaiacol in the generated samples were available. Therefore, a calibration curve

covering a wide range (1-500 μg/ml) was used to attempt the quantification. Afterwards,

a set of known concentration solutions of guaiacol were used to obtain a calibration

curve. The concentration obtained on the quantitative analysis were further adjusted

using the recovery and dilution as seen in Equation 3.

𝑦𝑖𝑒𝑙𝑑 𝑤𝑡% = 𝑚𝑎𝑠𝑠 ℎ𝑦𝑑𝑟𝑜𝑐ℎ𝑎𝑟

𝑚𝑎𝑠𝑠 𝐿𝑖𝑔𝑛𝑖𝑛× 100

15

Equation 3- Normalization of the concentration calculated

Eq 3

3.5 Quality assurance and quality control for the GC-MS

The used GC-MS method showed a small amount of carry over to the subsequent

samples on the run sequence. This error was only possible to determine for the screening

of the calibration curve when a solution of 500 µg/ml. An error of the procedure was

carried when the blank solution was put after the 500 µg/ml solution. Therefore, the

blank base peak areas of guaiacol and p-cresol were the higher values of the

chromatogram. The carry-over was avoided adding a blank solution in-between the

sequence.

Moreover, a short procedure was held preparing a blank with 40 ng/ml of the

phenanthrene D10 to observe the carry over during the calibration curve preparation. It

was observed that in the first solution was phenanthrene D10 present and, therefore, the

carry-over was confirmed.

The used recovery calculation method for guaiacol was a rough estimative due

to the lack of chemical similarity between the surrogate standard and the guaiacol. In

addition, matrices effects were not estimated while using the pure surrogate standard.

Another important aspect to discuss was the possibility of having non-ideal

results due to the decomposition of the samples. Samples 2L2, 3L0-3L4, 4L3 and 4L4

had apparent problems on the first chromatography injections. This repetition could

contain errors due to the stability of the samples which were not assessible.

The assessment of the blank samples used during this project were considered

an important aspect on the quality assurance and quality control. Despite the carry over

problem presented, the blanks were considered acceptable to assure that no

contamination happened. Mismatches and false positive were discussed on the Appendix

2 and Appendix 3.

4. Results

4.1 Analysis of provided lignin samples - pH measurements, solid particles, ash

content and non-volatile content

4.1.1 pH measurements, solids, ash content and non-volatile residue

The pH measurement values of the provided samples are presented in Table 4.

The measurements for the samples could not be repeated for four weeks due to

equipment’s issues. However, the sample DA-280-12 was the only sample that were

analyzed twice, and the pH values varied from 7.69 to 7.79. Therefore, the first

measurement is presented in Table 4. However, a pH measurement of the sample DA-

280-12 was made as a practice for handling the following samples. This measurement

was conducted in a sub-sample that was defrosted in a water bath and provided a pH of

4.68.

Table 5 provides the results for the solids particles, ash content and non-volatile

residues. The DA-280-12 ash analysis for the paper filter of 0.45 μm were performed

twice and no ash was measured. The results presented in Table 5 were not enough to

determine an effect of the temperature or type of lignin used. The solid particle results

of the alkaline lignin for both paper filters 10 μm and 0.45 μm showed a much higher

standard deviation than the dealkaline results. The ash results for the paper filter of

𝐶𝑜𝑛𝑐𝑓𝑖𝑥𝑒𝑑 =𝐶𝑜𝑛𝑐𝑐𝑎𝑙𝑐𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑦

∗ 𝐷𝑖𝑙𝑙𝑢𝑡𝑖𝑜𝑛 𝐹𝑎𝑐𝑡𝑜𝑟

16

10 μm showed similar results for both DA-280-12 (1.6 mg) and DA-300-12 (1.5 mg).

While the ash results for the paper filter of 10 μm showed similar results for the ALK-

300-12 (2.7 mg) and ALK-280-4 (3.0 mg). Apparently the ALK-280-4 had the higher

standard deviation values for the assays presented in Table 5. The non-volatile residues

percentage is equivalent of (g NVR/100 g of water-phase).

Table 4 - pH values for the first measurement. The measurement was performed over once every week for four weeks. However, the standard deviation calculated was very low and basically insignificant. Therefore, just the first values were presented.

pH

DA-280-12 7.69

DA-300-12 7.92

ALK-300-12 9.38

ALK-280-4 9.23

Table 5 - Solid particles analysis and ash content for the different paper filter used 10μm and 0.45μm; Non-volatile residues analysis for the provided samples. Means values and standard deviation used.

Samples 10μm Solids

particles (mg)

0.45μm Solids particles

(mg)

10μm Ash

(mg)

0.45μm Ash

(mg)

Non-

volatiles

residues

(%)

DA-

280-12

3.3±0.41 3.8±0.21 1.6±0.062 0.00 0.58%±0

.0033

DA-

300-12

2.1±0.15 1.6±0.49 1.5±0.19 1.2±1.6 2.4%±0.

056

Alk-

300-12

2.3±0.78 3.5±2.1 2.7±0.34 1.8±0.33 0.83%±0

.0020

Alk-

280-4

5.1±1.3 5.4±3.1 2.9±0.95 4.3±2.3 3.8%±0.

18

4.1.2 GC-MS

The GC-MS of the provided samples were necessary as a way of validating the

GC-MS method used for the generated samples. Therefore, one sample was chosen to

obtain the needed information. Sample DA-280-12 was tested undiluted, diluted 10

times and diluted 20 times to observe the saturation of the peaks. This analysis identified

the need of diluting the sample in 10 times.

Table 6 - GCMS Non-target analysis of DA-280-12. The retention time representing an important parameter for identifying samples and the match factor of the library software while identifying each species

Retention

Time

Match factor

(%)

Compound name Base peak area (% of

total)

13.3251 61 Phenol, 2-methoxy- (guaiacol) 8.42

16.5816 85.8 Catechol 6.98

13.0272 95.1 p-Cresol 6.39

9.9938 70.9 Cyclopropylacetylene 4.76

13.3532 57.8 Catechol 4.75

7.9345 83.9 Cyclopentane, 1,2,3,4,5-pentamethyl- 4.28

16.4758 96 2-Methoxy-5-methylphenol 4.05

8.8589 67.3 4-Octene, 2,6-dimethyl-, [S-(E)]- 3.93

12.3277 95.9 O-Cresol 2.98

17

Therefore, prior to the non-target analysis GC-MS, the sample DA-280-12 was

diluted 10 times, filtered and a liquid extraction with DCM was conducted. The analysis

was able to identify 543 species and the full data set can be found in Appendix 4.

Hydroxybenzenes species were more frequently found in this sample. The results were

organized according to the base peak area percentage related to the total base peak areas.

There were nine compounds with base peak area percentages higher than 2 % and they

were listed in Table 6. The three compounds that had higher base peak area percentages

were guaiacol (8.42 %), catechol (6.98 % and 4.75 %), p-cresol (6.39 %). The species

had a total area percentage of 26.54 %. Those compounds were possible candidates to

be quantified during the analysis of the samples generated.

4.1.3 ICP-MS / ICP-OES

The inorganic analysis of the provided samples was performed to obtain

information on the possible effect of the temperature, and it was only conducted on the

samples that were used in the same feedstock as the generated samples, dealkaline lignin.

As mentioned in the introduction section, sodium and sulfur were likely to be in the

dealkaline lignin samples. Sodium and sulfur discharged in the environment may

represent problems due to toxicity and sulfur may represent problems with corrosion.

The provided samples DA-280-12 and DA-300-12 results were compiled in Table 7.

The concentrations of sulfur and sodium were higher in the 300 °C sample compared to

the 280 °C. Also, the concentration of sodium in both samples were much higher than

sulfur. It was not possible to compare the concentrations with other studies in the

literature, since no study performed such water-phase analysis. However, a study

performed by Catalkopru et al. 2017 where three different biomass sources were

analyzed identified a maximum of 2.264 g/l of sodium in the water-phase 66. Compared

to this study, the identified sodium concentrations in the provided samples were around

24-35 times higher. The reason for this could be that the higher temperature processes

presented a higher concentration of elements which could relate to the increase in

solubility of the elements while the temperature of the solvent increases.

Table 7 - Sulfur and sodium concentration in the provided samples.

Samples S Na

DA-280-

12

10.86 56.20 g/l

DA-300-

12

14.37 79.73 g/l

4.2 HTC operation –Hydrochar yield

The hydrochar produced by the DA-280-12 is rich in carbon (around 80 %), the

carbon percentage in relation to the total carbon input from the lignin was only 38 %.

Which means that around 62 % of total carbon loaded is in the water and gas content.

This was an interesting information that showed the amount of carbon contained in the

water-phase. Therefore, a great part of carbon of the feedstock have not been utilized.

The first impact of the recycling that could be observed was that the cleaning

process became easier through the cycles. The char tends to get stuck in the reactor and

the cooling coil when the process is done. However, after the first recycle it was possible

to remove the hydrochar from these spots easier than after the first run.

The HTC operation generated samples every day for four weeks and the full data

sheet can be found in the Appendix 5. Each week corresponds to a replicate of the

experiment. Table 8 presents the mean hydrochar yield for each run. The run 0

corresponds to the first run on every week (1L0, 2L0, 3L0 and 4L0). The hydrochar

18

yield for the 1L0 (36.10%) was lower than the other results, which were around 48-53%.

The reason for the difference was not known, potentially it could be due to insufficient

cleaning of the reactor or inaccurately conducted filtering of the slurry after HTC

processing, since this was the first experiment made. The removal of the value resulted

in a lower standard deviation. Therefore, another mean was calculated (0*) excluding

the 1L0. The author acknowledge that the cleaning was not thorough, and it differed

from the standard procedure adopted for obtaining of the other samples.

Table 8 - Hydrochar yield of the samples 1L0-4L4 combined into run for every week. Each run represents a mean of values with their respective standard deviation

Run number Hydrochar yield (mean ± STDev)

Run 0 44.79% ± 5.019

Run 0* (excluding 1L0) 47.68% ± 0.1970

Run 1 49.98% ± 2.992

Run 2 49.65% ± 0.3972

Run 3 51.14% ± 0.6061

Run 4 50.98% ± 1.3873

The results for the hydrochar yield for the generated samples showed an increase

from the run 0 to the run 1 from 44.79 % to 49.98 %. However, it was possible to

determine that the values increased for every cycle. Also, the run mean values

demonstrated that the increase ranged from 44.79 % to 50.98 %. The literature showed

essentially that the water-phase recycling in the HTC process increases the hydrochar

yield 57,64–66. The increase for the most variable biomass sources variates. Some

recycling presented an increase of around 3 % over 4 cycles 64, while other presented a

bigger increase of around 10 % 57 in the first cycle and remained almost constant on the

subsequent cycles. The hydrochar yields in the literature variate from 55-76% according

to the process and the biomass used. Therefore, the generated samples provided a lower

hydrochar yield of a maximum of 50.98% on the run 4 mean value compared to

literature.

4.3 Analysis of generated samples

4.3.1 pH measurement

In addition to the pH measurements of all samples, the MQ water and the

dealkaline lignin dissolved in deionized water were measured pH 6.35 and pH 3.49,

respectively. The pH values for the generated samples can be found in Table 9 and they

varied from 4.28-4.67. The values were produced in the weekly runs. Once again,

Catalkopru et al. 2017 performed a pH analysis of the water-phase generated, and the

values increased from 3.9-4.1, 3.8-3.9, 5.5-5.7 for three different utilized biomasses.

Stemann et al. 2013 analyzed the pH over the recycling of poplar wood chips in the HTC

and the values remained constant at pH 3.4 The pH results of Table 9 display an increase

from 4.28 to 4.67 on the mean values. The water-phase pH may not depend much on the

process parameter but on the biomass used.

Table 9 - pH measurements of the samples 1L0-4L4 and the mean of each week combined into the run o-4

Sample pH Sample pH Sample pH Sample pH Run (mean)

pH (mean ± STDev)

1L0 4.50 2L0 4.25 3L0 4.22 4L0 4.15 Run 0 4.28±0.153

1L1 4.48 2L1 4.36 3L1 4.29 4L1 4.33 Run 1 4.37±0.0818

19

1L2 4.59 2L2 4.44 3L2 4.47 4L2 4.45 Run 2 4.49±0.0695

1L3 4.67 2L3 4.48 3L3 4.57 4L3 4.51 Run 3 4.56±0.0838

1L4 4.77

3L4 4.67 4L4 4.58 Run 4 4.67±0.105

4.3.2 GC-MS

The results of the generated samples were extensive, and the complete sets of

results can be found in the Appendix 4. The results in this part of the section were

organized according to the compounds with higher base peak area percentage. Table 10

presents the compounds that were more often present in all the samples with base peak

area percentage higher than 1 %, organized according to descending base peak area

percentage. Phenolics with methoxy groups species were amply detected in most of the

samples. The base peak area percentage of 1 % was chosen to be a cut-off valuable due

to the relative abundance to the other species. It was assumed that higher base peak area

percentages meant higher abundance. The base peak area percentage was calculated with

the base peak area divided by the total base peak area sum. The base peak area

percentage of the guaiacol was always much higher and the values were around 50 % of

the total base peak areas.

Table 10 - Most common compounds found in the samples generated ordered according to the base peak area percentage from higher to lower. The different compounds found in the samples generated are not ordered.

Common Compounds in samples 1L0-4L4

with base peak area >1 %

Different Compounds Found in samples

1L0-4L4 with base peak area >1 %

Guaiacol 2,3-Butanedione

Vanillin 2-Imidazolidinone

Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- Benzenepropanol, 4-hydroxy-3-methoxy-

Guaiacol, 4-butyl- 4H-1,2,4-Triazol-4-amine

Phenol 1,3-Butadiyne, 1,4-difluoro-

Syringol Methane-d, trichloro-

5-methyl guaiacol Cyclotetrasiloxane, octamethyl-

There were more different compounds found over the 1 % cut-off and they are

not listed in Table 10 but can be found in the full data set. A mismatch of the library

software and injection problems could cause the differences in the found compounds.

Nonetheless, they will not be further discussed in this report due do the difficulties in

determining the source of the species. Table 11 can be used to see the recovery of the

internal standard.

Table 11 - Recovery calculation due to losses in filtration and liquid-liquid extraction. Recovery calculation due to losses in filtration and liquid-liquid extraction

Sample Recovery Sample Recovery Sample Recovery Sample Recovery

1L0 25.3% 2L0 3.44% 3L0 43.9% 4L0 0.195%

1L1 2.93% 2L1 1.37% 3L1 17.2% 4L1 0.467%

1L2 3.33% 2L2 13.4% 3L2 25.6% 4L2 0.264%

1L3 2.75% 2L3 0.265% 3L3 18.1% 4L3 2.59%

1L4 0.833%

3L4 21.4% 4L4 8.72%

The recoveries varied distinctively, and no pattern was observed. The recovery

values were an important tool to assess the selected method of quantification. The high

variation observed gave information that this might not be the best method for

quantification of the samples 1L0-4L4. However, a quantification was performed for the

20

guaiacol to have an estimation of the concentration level. Table 12 displays the means

and standard deviation calculated for each run. The standard deviation was for most of

the samples higher than the mean values. Therefore, it was not possible to evaluate the

accuracy of the experiment.

The GC-MS results of the sample DA-280-12 and sample 1L0 were compared.

There were evident differences in the composition found in the sample DA-280-12 and

the samples 1L0-4L4. Catechol showed a higher relative abundance in the sample DA-

280-12 than the samples 1L0-4L4, while vanillin was not detected in the sample DA-

280-12. A better discussion will be given further in the discussion section.

Table 12 - The concentration of guaiacol after quantification and normalization using calibration curve, recovery % and dilution factor.

Run Number Guaiacol Concentration (mg/mL)

Run 0 9 ± 14

Run 1 3 ± 3

Run 2 6 ± 9

Run 3 6 ± 8

Run 4 2 ± 1

Saisu et al. 2003 studied the decomposition of lignin on water-phenol mixtures

at 399 °C with 0-60 min reaction times. The authors identified a list of compounds,

presented in Table 13, that were generated during the process in the presence and the

absence of phenol. The phenol/lignin ratio inhibited the polymerization, char formation,

of the tetrahydrofuran insoluble products. Also, syringol yield was drastically reduce in

the presence of phenol over time while catechol increased yield in the presence of

phenol. Which means that ether groups directly connected to phenolic rings were more

hydrolyzed in the presence of phenol for longer periods of time. The compounds

syringol, guaiacol were found in the samples 1L0-4L4. While some compounds such as

methoxycatechol, o-cresol and p-cresol were found in some of the samples. The

conclusion is that species that were found only in the presence of phenol could be found

in the samples that did not went through a recycling of the water-phase such as DA-280-

12, 1L0, 2L0, 3L0 and 4L0.

Table 13 - Tetrahydrofuran soluble compounds found after treating lignin in a water phenol mixtures media at

400°C up to 60 min (Source: Saisu et al 2003)

Presence and absence of phenol Only in presence of phenol

Syringol o-cresol

Methylsyringol p-cresol

Ethylsyringol 2-ethyl-phenol

Guaiacol 4-ethyl-phenol

Ethylguaiacol xanthene

Acetoguaiacol 2,2-dihydroxymethane

catechol 2-hydroxyphenylguaiacol

Methoxycatechol

4.3.3 ICP-MS/ICP-OES

The analysis of the generated samples was compiled in Table 14, for sodium and

sulfur, respectively. It was possible to state that the concentration of sodium and sulfur

increases during the recycling of the water phase during the HTC process.

The samples provided used 100 g of lignin as feedstock and the generated

samples used 25 g. This difference in the lignin input affected the concentration of

21

sodium and sulfur obtained in the water phase. It was important to understand that the

concentration would be higher if no liquid was evaporated throughout the process and

the whole liquid recycling. Table 15 shows the increase on the concentration of sodium

and sulfur for every cycle. It was possible to observe that the concentration increases in

every cycle and the increase reduce from 50.67 % in cycle 0-1 to 6.91 % in cycle 3-4.

Table 14 - Sodium and sulfur concentration analyzed by ICP-MS and ICP-OES, respectively. The values were presented as mean ± standard deviation.

Run Na conc (g/l) S conc (g/l)

0 8.75 ± 0.0426 2.14 ± 0.156

1 13.8 ± 0.0303 3.23 ± 0.177

2 19.2 ± 0.111 4.42 ± 0.256

3 21.6 ± 0.0244 4.74 ± 0.109

4 22.9 ± 0.148 5.06 ± 0.429

Table 15 - Variation in concentration values of Na and S concentration highlighted for every cycle.

Cycle Increase in Na Increase in Sulfur

0-1 57.8% 50.7%

1-2 38.9% 37.0%

2-3 12.5% 7.10%

3-4 6.18% 6.91%

4.4 Microalgae recycling

The hydrochar yield was presented in Table 16. All replicates increased in the

hydrochar yield over the recycles. It could be observed that there was an increase of

26.80 % on the first recycle. The experiment was complicated to perform since the used

reactors were small and composed of three small pieces. It was common that the pieces

were hard to detach from each other after the experiment and mechanic forces were used

to disassemble the reactors. Despite the difficulties with the reactors, the obtaining of

the hydrochar was not affected but some of the water-phase was lost in this procedure.

The first run of the microalgae sample was also characterized in the GC-MS and the

results are compiled in the Appendix 5. The main species found in the samples were

pyrazines. However, guaiacol, vanillin and phenol were also present in the microalgae

sample.

Table 16 - Microalgae HTC experiment results. Hydrochar masses obtained in first run and first recycle for the different replicates. The increase was also displayed in percentage and the mean values and standard deviation were presented in the last row.

Experiment First run (g) First recycle (g) Increase (%)

1 0.615 0.765 24.4

2 0.570 0.763 33.9

3 0.655 0.800 22.1

Mean ±

STDev

0.613 ± 0.0425 0.776 ± 0.0208 26.8 ± 6.22

5. Discussion

The results generated in this study provided new information about the water-

phase composition of a hydrothermal carbonization process that used lignin as

22

feedstock. It was shown which species were present in higher abundance in most of the

samples. In addition, this study provided information that the recycling of the water-

phase had the potential to increase the hydrocar yield of the processes using lignin as

feedstock and microalgae as feedstock.

5.1 Recycling results discussion – Hydrochar yield and composition change over

recycling

The yield of the hydrochar was a key factor to the success of the recycling

process. The recycling should not affect negatively the yield in order to make it feasible.

The values were listed in Table 8 and they ranged from 47.68-51.14 %, except

1L0 (44.79%), showing an increase in the yields in the first recycle and remained

basically constant through the subsequent cycles. Although the highest mean (51.14%)

was detected on the third recycle mean, the fourth recycle mean had higher standard

deviation related to the third recycle. The conclusion was that there was a small increase

(around 6 %) on the hydrochar yield over the recycling. This increase could be higher

when using higher amounts of feedstock.

The quantification of guaiacol was a rough estimation due to the lack of a proper

surrogate standard. The analysis of the means was complex and presented a high

variation of the replicates from 0.14 - 34.92 mg/ml. It was not possible to draw a

conclusion. The full data can be seen in the Appendix 6.

5.2 Differences between the provided samples and generated samples

The analysis made on the provided samples were used as a starting point to

understand how to deal with the water-phase. The solid particle analysis, ash content

and non-volatile residues did not bring much information. It was not possible to draw

conclusions on the influence of the feedstock, temperature and reaction time of the

process for these three analyzes. It would be necessary to conduct a broader study with

a more elaborate experimental design. However, it was possible to draw some

conclusion with the pH analysis.

Apparently, the difference on using the precursor with an alkaline treatment can

get a difference on the pH of the sample of almost 1.46 units from 7.92 to 9.38. Looking

at the temperature effect, the DA-280-12 showed a pH of 7.79 and the DA-300-12

showed a pH of 7.92. However, the conclusions should be considered with caution due

to the limited number of samples.

The pH measurements performed on the DA-280-12 and DA-300-12 samples

provided values of pH around 8.0, while the analysis of the samples 1L0-4L4 provided

pH values of around pH 4.28-4.67. These differences demonstrated that decomposition

reactions occurred within the samples. It was believed that the differences in the

parameters were the cause to generate different species and provided a different pH

value. Therefore, it would be possible to control the parameters of the HTC to obtain

specific products such as catechol or vanillin.

The divergence on the results were evident. The sample DA-280-12 presented

mainly hydroxybenzene species while phenolics with methoxy groups were mainly

found in the samples 1L0-4L4. Sample 1L0 presented guaiacol, vanillin and ethanone,

1-(3-hydroxy-4-methoxyphenyl)-, sample DA-280-12 presented a higher amount of

catechol (11.73 %), p-cresol, o-cresol and guaiacol. Moreover, p-cresol and o-cresol

showed on sample 1L0 with 0.57 % and 0.03 %, respectively. While catechol was not

detected on the sample 1L0. Even though there were differences in the reaction

parameters of the samples (precursor amount, temperature and reaction time). The

results were compared to obtain some comprehension of composition on both samples.

23

Already in 1985, Vuori and co-workers conducted a study of the thermal

degradation of the guaiacol to understand the degradation of the lignin monomers. The

C-O bond present in the methyl group was evaluated to be 247 kJ/mol, being the most

vulnerable part of the guaiacol molecule 98,99. A thermo degradation of the guaiacol

generated mainly catechol, o-cresol and phenol 98, while its selectivity reduced when the

reaction time increased. Therefore, the information provided by 98 could be used to

manipulated the formation of catechol, o-cresol and phenol.

Vanillin was the second most abundant component of the water-phase in the

samples 1L0-4L4. Its synthesis can be made from the reaction of guaiacol and glyoxylic

acid 100. It is a compound that is sensitive to light, reacts with singlet oxygen and

decomposes with heating producing CO and CO2 100. The photodegradation in presence

of hydrogen peroxide of lignin derivates compounds was favored by the presence of α-

carbonyl and phenolic groups 101 and the reaction of vanillin with singlet oxygen, excited

state of molecular oxygen (O2) also promotes decomposition 102. Therefore, it was

possible to deduce that the decomposition of vanillin will, most likely, generate

guaiacol 103. However, vanillin can also generate 4-methylguaiacol, which was one of

the compounds found in both samples in lower relative abundance 104.

Addressing the third most abundant compound in the samples 1L0-4L4,

ethanone, 1-(3-hydroxy-4-methoxyphenyl)-, also known as isoacetovanilone. Its

structure is similar to the vanillin and it is an isomer of the acetovanillone, also known

as apocynin, was identified on the sample 1L4. However, most of the samples 1L0-4L4

identified the isomer, apocynin. It was concluded that the apocynin was a mismatch of

the library software. Therefore, it is likely to produce the same compounds during

decomposition. Figure 5 shows the chemicals structure for the vanillin and ethanone, 1-

(3-hydroxy-4-methoxyphenyl)- compared to the coniferyl alcohol. Vanillin was

generated from coniferyl alcohol while the ethanone, 1-(3-hydroxy-4-methoxyphenyl)-

had the hydroxyl and methoxy group positions switched. The author could not identify

the origin of the ethanone, 1-(3-hydroxy-4-methoxyphenyl)- molecule.

Figure 5 -Structures of the molecules: Coniferyl alcohol, vanillin and ethanone 1-(3-Hydroxy-4methoxyphenyl). The

figure tries to identify the source of the molecules found in the water-phase comparing with one of the monomers

that forms the lignin molecule.

The use of lignin as feedstock in the HTC process can be used to obtain

hydrochar and water-phase. This water-phase had mainly aromatic species that are

commonly obtained from other sources. Therefore, the use of a paper/pulp industry

waste as a source to obtain aromatic species such as vanillin, catechol and guaiacol is

possible.

5.3 Microalgae hydrochar yield discussion

The hydrochar yields were a primary demonstration that the recycling of this

feedstock is feasible and increases the yield of the hydrochar. No literature about

recycling the water-phase from an HTC process using microalgae was found.

Microalgae are microorganism and their production are low, and this was a key point to

increase the yield of the hydrochar of HTC. Although the microalgae samples were

24

limited, the experiments were still able to be performed and showed that the hydrochar

yield increased.

The composition of the microalgae showed several pyrazine derivates

compounds, guaiacol, vanillin and phenol. Although lignin was not present on the

microalgae structure, guaiacol, vanillin and phenol were present in the water-phase.

Microalgae are composed by proteins which contain units of aromatic rings on many of

the molecules such as tyrosine, phenylalanine and tryptophan. Phenylalanine and

tyrosine can be used to obtain vanillin on a complicated biosynthesis pathway 100,105.

The pyrazine can be produced by many pathways. The author deduced that the

pyrazine derivates were produced from glutamine or asparagine, two amino acids that

constitute some proteins. The literature led to believe that starch and cellulose derivates

would be shown on the results. However, the amino acids units demonstrated to be

important for the HTC process of the microalgae.

5.4 Sodium and sulfur concentration

There were three evaluations made: the influence of the temperature, the

difference on the amount of feedstock and the increase on the concentration during the

recycling. The first point noticed was that, apparently, the temperature of the process

influenced on the concentration of Na and S in the water-phase. Sodium increased

around 32 % and sulfur increased around 42 % when the process temperature increased

from 280 °C to 300 °C. However, it was not possible to be certain of this relation due to

lack of experimental data.

The samples DA-280-12 and DA-300-12 had a lignin input of 100 g, which was

four times more lignin than in the generated samples, 25g. The concentration of Na of

the samples DA-280-12 and DA-300-12 in relation to the generated samples were

around 6 times and 9 times higher, respectively. While the concentration of sulfur of the

samples DA-280-12 and DA-300-12 in relation to the generated samples were round 5

times and 6.7 times higher, respectively. It was expected to increase in at least 4 times

the concentration of those elements due to the increase on the feedstock. Apparently,

higher process temperature increased the concentration of the inorganics.

Table 14 provided information to identify the relation between the recycling and

the concentration. They were similar, when comparing the elements, with exception for

the cycle 2-3 that had an almost a double increase in the Na concentration than S

concentration. The decaying increase rate over the recycles made it possible to conclude

that the increase would cease at some point and the elements were getting concentrated

on the char. The determination of this increase and the limit of increase could be another

possible research for the future. The increase of the concentration of sodium and sulfur

could be problematic, and it may be necessary to apply a treatment on the feedstock to

reduce the concentration of those inorganics.

6. Conclusions and Outlook

The project was designed to evaluate the water-phase of the hydrothermal

carbonization process using lignin and microalgae as feedstock. Also, trying to evaluate

the properties and composition changes over the recycling of the water-phase.

Guaiacol, vanillin and ethanone, 1-(3-hydroxy-4-methoxyphenyl)- were the

species with the highest component peak area in the samples. Also, those species were

probably decomposed over time. The possibility of extracting valuable chemicals, e.g.

guaiacol and vanillin, from a concentrated water-phase should be studied. Lignin is a

natural source of aromatics and it should be exploited more frequently to avoid e.g. use

of fossil fuels. It may be possible to increase the concentration of all compounds present

in the water-phase. This could be done by increasing the feedstock input, by changing

25

the process parameters (temperature and reaction time) or by increasing the number of

recycling cycles.

The recycling of the water-phase on the HTC process without reducing the

hydrochar yield was possible. The use of microalgae as feedstock to the process was

also demonstrated to be feasible and the recycling did not show any drawback to the

hydrochar yield. However, future work should be conducted with microalgae due to its

potential.

This represents a cost reduction for the HTC due to water input reduction.

However, it was not possible to determine the limit that the water-phase can be recycled

without drawbacks to the process such as reduction in hydrochar yield or decrease of the

quality of the hydrochar. It is estimated that drawbacks are real such as concentration of

toxic species and low quality of hydrochar. The water-phase showed signs of increasing

the concentration of inorganics. This could be a future problem for the treatment prior

to discharge. Future work could be conducted to determine a correlation that relate

temperature and process time to the concentration of sodium and sulfur.

The water-phase analysis assessed a possible decomposition of the species that

are present in the water-phase samples that came from lignin. The pH variation was

from 4.28 to 7.79. While the pH did not variate much during the recycling of the water-

phase. The variation of the pH values of the samples could be related to the

decomposition of the species within the water-phase. Since the samples 1L0-4L4 were

handled and measured at the same time the pH values variate from 4.15-4.77. Also, the

pH tends to increase slightly for every recycle, which can mean that the recycling

increased the concentration of a determined species that increases the pH. It was not

possible to draw a conclusion on the solids and non-volatile residue evaluation.

An important conclusion was that the methods associated with the GC-MS,

injection and library search, should be optimized. The used methods did not reproduce

values with a reasonable reproducibility. The GC-MS was chosen for the non-target

analysis. Therefore, it maybe be necessary to choose a different method for the

quantification of species found in the water-phase. A liquid chromatography (LC)

technique would be more interesting such as high-performance liquid chromatography

(HPLC). The use of this technique would dispense the necessity of the liquid-liquid

extraction.

This study provided information that the water-phase of the hydrothermal

carbonization process should not be neglected, as seen in the literature. It was possible

to find valuable products within the water-phase. Also, it was essential to show that

reusing the water in the process can be possible, since this resource is essential for life

and its’ demand increases every year.

Acknowledgement

First, I would like to thank God for everything in my life.

I am extremely grateful to Stina Jansson for the opportunity. I would like to

thank all the researcher group for the support and help. Next, I thank Kenneth Latham

for assisting me. Also, I thank the SLU for providing the microalgae samples.

I gracefully thank Andriy Rebryk for all the support regarding the GC-MS

operation. I also thank Erik Björn for the assistance and training regarding the operation

of the ICP-MS and ICP-OES equipment. I am eternally grateful to my parents for the

unconditional support, without them this I would not be able to accomplish this goal.

Finally, I thank my fiancée Arielle for loving me and listening to my complaints

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31

Appendix

Appendix 1 – Instrumental Parameters and procedures

Pre-treatment

The samples were diluted with deionized water in a ratio of 1:10, phenanthrene

D10 was added to obtain concentration of (40ng/ml). Afterwards. the samples were

filtrated and a liquid-liquid extraction with dichloromethane (DCM) was conducted. The

liquid-liquid extraction was made with a 1-1 ratio of sample and solvent. The volume

was collected, and anhydrous sodium sulfated was added to the solution and gently

mixed. The solution was let to rest and separate.

GC-MS parameters

The sample collected after extraction was sent to analysis in a gas

chromatographer Agilent Technologies 7890B GC System with columns; 122-5511 DB-

5MS, 15 m x 0.25 mm, 0.1 Micron, 122-5532UI DB-5MS UI, 15 m x 0.25 mm, 0.25

Micron. Each analysis a 1 μl sample was injected into the GC-MS system at initial

column temperature 40℃, holding for 2 min, ramped to 300°C with 5°C/min; holding

for 2 min. The injector was kept at 300°C in splitless mode with the carrier gas helium.

The ion source was maintained at 230°C. Mass spectrometric measurements were

performed using electron impact ionization (EI) at an ionizing voltage 70 eV, and a

scanning minimum of m/z 30.

32

Appendix 2 – False positive identified

Samples 3L2 and 3L4 identified 2-n-Butyl furan as the species with the second

highest component area. The species have a retention time of 13.056 min which was a

close match to the guaiacol, around 13.060 min. The software was checked for

alternative hits and guaiacol could not be found. Therefore, it was hard to understand

the root of the error.

Mismatches were identified throughout the evaluation of the results. As well as

a false positive was identified, and it will be shown below.

Figure 6 - Original spectra RT 13.056min of sample 3L3

33

A specific search was conducted using this spectra fragment:

Figure 7 - Individual search on Library software.

Figure 8 - Matched compound: Guaiacol (mainlib) Phenol, 2-methoxy-

10 20 30 40 50 60 70 80 90 100 110 120 130 1400

50

100

1527

39

41

53

5563

77

81

91 95 105

109

121

124

O

HO

(Text File) +EI Scan (rt: 13.056 min) Frag=70.0V 20190411_29_3L3.D

10 20 30 40 50 60 70 80 90 100 110 120 130 1400

50

100

53

55

65

67 74

77

81

92

95

109 124

+EI Scan (rt: 13.056 min) Frag=70.0V 20190411_29_3L3.D Phenol, 2-methoxy-Head to Tail MF=850 RMF=854

10 20 30 40 50 60 70 80 90 100 110 120 130 140

0

50

100

50

100

15 27 29 3139

41 43

46 49

52

53

53

55

55

62

63

63

64

65

65

67

67

69

69 73

74

75

76

77

77

80

80

81

81

82

82

83 86 90

91

92

93

95

95

97 104

105

109

109

121

121

124

124

34

Figure 3 - Spectra fragment RT 13.0567 min obtained on automatic search

35

Figure 10- false positive identified: Tetrazolo[1,5-b]pyridazine

N

N NN

N

36

Appendix 3 – Mismatches list

Table 17 - Compounds that were believed to be mismatches. The software identified the actual species as alternative match.

Mismatch Actual Species

4-Hydroxy-2-methoxybenaldehyde Vanillin Benzaldehyde, 2,4-dihydroxy-6-methyl-

Vanillin

Apocynin Ethanone, 1-(3-hydroxy-4-methoxyphenyl)-

2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)-

Guaiacol, 4-butyl-

2-Acetyl-5-methylfuran Phenol, 2-methoxy-

37

Appendix 4 - GC-MS SPECTRA

Table 18 – GC-MS results for the sample DA-280-12 ordered from higher base peak area to lowest.

RT Compound name Base peak area Area %

13.325 Phenol, 2-methoxy- 1E+08 8E+00

16.582 Catechol 8E+07 7E+00

13.027 p-Cresol 7E+07 6E+00

9.9938 Cyclopropylacetylene 6E+07 5E+00

13.353 Catechol 5E+07 5E+00

7.9345 Cyclopentane, 1,2,3,4,5-pentamethyl- 5E+07 4E+00

16.476 2-Methoxy-5-methylphenol 5E+07 4E+00

8.8589 4-Octene, 2,6-dimethyl-, [S-(E)]- 5E+07 4E+00

12.328 Phenol, 2-methyl- 3E+07 3E+00

18.912 Phenol, 4-ethyl-2-methoxy- 2E+07 2E+00

8.9045 Sulfurous acid, di(cyclohexylmethyl) ester 2E+07 2E+00

9.0872 4-Octene, 2,6-dimethyl-, [S-(E)]- 2E+07 2E+00

7.1473 Styrene 2E+07 1E+00

30.085 2,6-Diisopropylnaphthalene 2E+07 1E+00

29.983 2,6-Diisopropylnaphthalene 2E+07 1E+00

17.734 Cyclopentanecarboxamide, N-methallyl- 2E+07 1E+00

6.939 Acetic acid, 2-[2-(2-acetoxy-ethoxy)-phenoxy]-ethyl ester

1E+07 1E+00

8.0212 1,5-Heptadiene, (E)- 1E+07 1E+00

8.0189 3-Hexene, 3-ethyl-2,5-dimethyl- 1E+07 1E+00

8.9027 2-Propenoic acid, ethenyl ester 1E+07 1E+00

15.834 Phenol, 4-ethyl- 1E+07 1E+00

6.2583 1-Buten-3-yne, 1-chloro-, (Z)- 1E+07 1E+00

15.89 Phenol, 3,5-dimethyl- 1E+07 1E+00

8.0266 2-Pyrazoline, 1-isobutyl-3-methyl- 1E+07 1E+00

15.778 Phenol, 4-ethyl- 1E+07 1E+00

16.347 2-Methoxy-5-methylphenol 1E+07 1E+00

10.368 trans-2,4-Dimethylthiane, S,S-dioxide 1E+07 8E-01

6.7388 2-Heptene, 5-ethyl-2,4-dimethyl- 9E+06 8E-01

16.087 Phenol, 2-methoxy-3-methyl- 8E+06 7E-01

8.1291 Ethane, 1,1,2,2-tetrachloro- 8E+06 7E-01

35.358 Panaxynone 7E+06 6E-01

28.984 2,6-Diisopropylnaphthalene 7E+06 6E-01

9.5609 3,4-dimethylfuran 6E+06 5E-01

14.896 Phenol, 2-ethyl- 6E+06 5E-01

22.332 Tetradecane 6E+06 5E-01

29.862 2,6-Diisopropylnaphthalene 6E+06 5E-01

18.45 1,2-Benzenediol, 3-methyl- 5E+06 5E-01

42.114 9-Octadecenamide, (Z)- 5E+06 4E-01

18.476 3-Ethylanisole 5E+06 4E-01

21.922 Benzene, 1,4-dimethoxy- 5E+06 4E-01

15.31 Phenol, 2,4-dimethyl- 5E+06 4E-01

28.806 2,6-Diisopropylnaphthalene 5E+06 4E-01

16.568 4-Undecene, 4-methyl-, (Z)- 4E+06 4E-01

10.09 Cyclotetrasiloxane, octamethyl- 4E+06 4E-01

38

35.125 3-(6-Methoxy-3-methyl-2-benzofuranyl)acrylic acid

4E+06 4E-01

8.3059 2,3'-Bifuran, 2,2',3',5-tetrahydro- 4E+06 3E-01

8.3038 Octane, 3-methyl-6-methylene- 4E+06 3E-01

19.653 Nonane, 2,2,4,4,6,8,8-heptamethyl- 4E+06 3E-01

15.248 Phenol, 2,4-dimethyl- 4E+06 3E-01

19.07 Phenol, 4-ethyl-2-methoxy- 4E+06 3E-01

18.475 Methylsulphonamide, N-ethyl-N-tetradecyl- 3E+06 3E-01

14.232 Hept-2-ene, 2,4,4,6-tetramethyl- 3E+06 3E-01

15.186 Benzene, 1,2-dimethoxy- 3E+06 3E-01

21.341 Phenol, 2-methoxy-4-propyl- 3E+06 3E-01

16.812 Nonane, 2,2,4,4,6,8,8-heptamethyl- 3E+06 3E-01

9.5817 Phenol, 4-ethyl-2-methoxy- 3E+06 2E-01

11.78 2-Cyclopenten-1-one, 2,3-dimethyl- 3E+06 2E-01

14.808 Phenol, 4-methoxy-3-methyl- 3E+06 2E-01

6.8756 3-Amino-s-triazole 3E+06 2E-01

14.18 Propanoic acid, anhydride 3E+06 2E-01

11.368 Cyclopentanone, 2-(1-methylpropyl)- 3E+06 2E-01

7.4632 Oxime-, methoxy-phenyl-_ 3E+06 2E-01

17.101 1,2-Benzenediol, O-(butoxycarbonyl)-O'-(isobutoxycarbonyl)-

2E+06 2E-01

10.699 1,3-Benzodioxole 2E+06 2E-01

6.8246 3-Ethyl-4-methyl-2-pentene 2E+06 2E-01

10.375 Piperoxan 2E+06 2E-01

11.696 2H-Pyran, 3,4-dihydro- 2E+06 2E-01

18.47 1,5-Hexadiene, 3,3,4,4-tetrafluoro- 2E+06 2E-01

14.267 4-Isopropylbenzenethiol, S-methyl- 2E+06 2E-01

38.966 Phenol, 4,4'-(1-methylethylidene)bis- 2E+06 2E-01

38.968 Benzoic acid, 2-(4-aminophenyl)- 2E+06 2E-01

11.371 Valeric anhydride 2E+06 2E-01

20.741 1H-Inden-5-ol, 2,3-dihydro- 2E+06 2E-01

12.765 Acetophenone 2E+06 1E-01

36.657 1-Cyclopenten-3-one, 1-(1-cyclohexen-1-yl)-2-[(carboxyethyl)(cyano)methyl]-

2E+06 1E-01

7.8416 Cyclohexane, 1-ethyl-2,3-dimethyl- 2E+06 1E-01

49.685 7H-Benzimidazo[2,1-a]benz[de]isoquinolin-7-one

2E+06 1E-01

36.277 Isoquinoline, 1-isobutyl- 2E+06 1E-01

20.179 Cyclohexane, (1,1-dimethylpropyl)- 2E+06 1E-01

18.965 4-Chlorobutyric acid, 4-isopropylphenyl ester 2E+06 1E-01

12.496 Pyrrolidine, 2-butyl-1-methyl- 2E+06 1E-01

38.171 Benzene, 1,1'-(2-pentene-1,5-diyl)bis- 2E+06 1E-01

24.868 Nonane, 2,2,4,4,6,8,8-heptamethyl- 2E+06 1E-01

13.04 1-Pentanone, 1-(2-furanyl)- 2E+06 1E-01

14.489 1-(Trimethylsilyl)-1-propyne 1E+06 1E-01

40.484 1-Phenylcyclopentanecarboxylic acid 1E+06 1E-01

17.326 Mequinol 1E+06 1E-01

9.4644 Ethanone, 2-(formyloxy)-1-phenyl- 1E+06 1E-01

14.374 Benzene, 1,2,4,5-tetramethyl- 1E+06 1E-01

13.034 Cyclopentene 1E+06 1E-01

39

19.709 Dichlorine heptoxide 1E+06 1E-01

42.542 Nonanamide 1E+06 1E-01

13.291 Benzene, 1,2,4,5-tetramethyl- 1E+06 1E-01

17.574 m-Guaiacol 1E+06 1E-01

24.326 Glycine, N-(2-fluorobenzoyl)-, propyl ester 1E+06 1E-01

28.35 Homovanillic acid 1E+06 1E-01

17.847 Phenol, 4-ethyl-2-methyl- 1E+06 1E-01

21.666 Dodecane, 2,6,10-trimethyl- 1E+06 1E-01

17.553 Phenol, 2-(1-methylethyl)-, methylcarbamate 1E+06 1E-01

31.208 Cyclononasiloxane, octadecamethyl- 1E+06 1E-01

15.313 Cyanic acid, phenyl ester 1E+06 1E-01

8.1598 Cyclopentane, 1,2,3,4,5-pentamethyl- 1E+06 1E-01

8.3575 4-Oxohex-2-enal 1E+06 1E-01

12.349 4,4'-Bi-1,3,2-dioxaborolane, 2,2'-diethyl- 1E+06 1E-01

13.512 Isomaltol 1E+06 1E-01

12.501 6-Hepten-3-one, 5-hydroxy-4-methyl- 1E+06 1E-01

20.714 (5R,8R,8aS)-5-Heptyl-8-methyloctahydroindolizine

1E+06 1E-01

19.907 3',5'-Dihydroxyacetophenone 1E+06 1E-01

18.916 1-Propanone, 1-(1-cyclohexen-1-yl)- 1E+06 9E-02

10.164 6-Isopropyl-2,3-dihydropyran-2,4-dione 1E+06 9E-02

38.765 Benzene, 1,1'-(2-pentene-1,5-diyl)bis- 1E+06 9E-02

22.418 4-Chlorobutyric acid, 4-isopropylphenyl ester 1E+06 9E-02

12.51 3-Nonen-5-one 1E+06 9E-02

7.4991 3,3-Diethoxy-1-propyne 1E+06 9E-02

11.561 Octane, 1,1'-oxybis- 1E+06 8E-02

34.195 Cyclodecasiloxane, eicosamethyl- 1E+06 8E-02

19.417 5-Oxotetrahydrofuran-2-carboxylic acid, ethyl ester

1E+06 8E-02

14.269 Benzene, 1,2,4,5-tetramethyl- 9E+05 8E-02

12.447 Benzene, 1,2,4,5-tetramethyl- 9E+05 8E-02

22.028 1-methyl-1-indanol 9E+05 8E-02

11.655 Valeric anhydride 9E+05 8E-02

19.854 Difluorophosphoric acid 9E+05 8E-02

19.852 Cyclohexane, tetracosyl- 9E+05 8E-02

9.2185 Thiazole 9E+05 8E-02

7.636 2-Cyclopenten-1-one, 2-methyl- 8E+05 7E-02

9.8401 trans-2,4-Dimethylthiane, S,S-dioxide 8E+05 7E-02

13.021 Benzoic acid, 2-methylpropyl ester 8E+05 7E-02

11.272 Difluoroisocyanatophosphine 8E+05 7E-02

12.897 Cyclotrisiloxane, hexamethyl- 8E+05 7E-02

18.469 Resorcinol, 2-acetyl- 8E+05 7E-02

27.853 Cyclooctasiloxane, hexadecamethyl- 8E+05 7E-02

7.2193 2-Thiopheneacetic acid, oct-3-en-2-yl ester 8E+05 7E-02

8.6813 Sulfurous acid, di(cyclohexylmethyl) ester 8E+05 7E-02

35.905 2-Fluorobenzoic acid, 4-methoxyphenyl ester 8E+05 7E-02

10.798 3-Heptene, 2,2,4,6,6-pentamethyl- 8E+05 7E-02

7.6937 2-Pyrazoline, 1-isobutyl-3-methyl- 8E+05 7E-02

18.843 Phenol, 3,4,5-trimethyl-, methylcarbamate 8E+05 6E-02

40

13.098 Benzene, 1,2,4,5-tetramethyl- 8E+05 6E-02

36.926 Cyclooctasiloxane, hexadecamethyl- 7E+05 6E-02

7.5282 2-Butanone, 1,1,1-trifluoro- 7E+05 6E-02

29.113 2,6-Diisopropylnaphthalene 7E+05 6E-02

23.605 4-Chlorobutyric acid, 4-isopropylphenyl ester 7E+05 6E-02

19.696 Phosphonic acid, methyl-, dipentyl ester 7E+05 6E-02

9.0406 3-Hydroxy-4-methoxybenzaldehyde, TBDMS 7E+05 6E-02

27.854 Phloroglucinaldehyde, tris(trimethylsilyl) ether 7E+05 6E-02

6.5123 p-Xylene 7E+05 6E-02

29.39 Dodecyl acrylate 7E+05 6E-02

11.359 1-(3H-Imidazol-4-yl)-ethanone 7E+05 6E-02

18.003 Phenol, 2-(1-methylethyl)-, methylcarbamate 7E+05 6E-02

17.704 4-Chlorobutyric acid, 4-isopropylphenyl ester 7E+05 6E-02

10.426 Benzene, 1,2,3-trimethyl- 7E+05 6E-02

13.218 2-Ethylbutyric acid, tetrahydrofurfuryl ester 7E+05 6E-02

19.24 But-2-enoic acid, amide, 3-methyl-N-methallyl- 7E+05 6E-02

9.5631 1-Pentyn-3-amine, 3-methyl- 7E+05 6E-02

35.373 Diheptylpentylamine 7E+05 6E-02

19.044 diethyl methyl phosphate 7E+05 6E-02

18.852 Undecane, 6,6-dimethyl- 7E+05 6E-02

19.099 1-Hydroxycyclohexanecarboxylic acid 7E+05 6E-02

13.797 Sulfurous acid, 2-ethylhexyl hexyl ester 7E+05 6E-02

19.565 Succinic acid, cyclohexylmethyl 2-methoxy-5-methylphenyl ester

6E+05 6E-02

34.267 Hexadecanoic acid, methyl ester 6E+05 6E-02

39.409 Cyclononasiloxane, octadecamethyl- 6E+05 6E-02

18.724 Phenol, 2,3,5-trimethyl- 6E+05 5E-02

13.014 Benzene, 1,2,3,5-tetramethyl- 6E+05 5E-02

12.685 Malonic acid, 3-methylpentyl octyl ester 6E+05 5E-02

20.084 Benzaldehyde, 2-ethyl- 6E+05 5E-02

35.82 1-Ethyl-2-methylquinolinium iodide 6E+05 5E-02

19.469 4'-Fluorovalerophenone 6E+05 5E-02

10.538 4-Octene, 2,3,7-trimethyl-, [S-(E)]- 6E+05 5E-02

12.246 Benzene, 1-methyl-4-propyl- 6E+05 5E-02

21.596 4-Amino-5-formamidomethyl-2-methylpyrimidine

6E+05 5E-02

20.955 3-Furancarboxylic acid, 2,5-dimethyl-, methyl ester

6E+05 5E-02

19.35 2-tert-Butylcyclohexyl methylphosphonofluoridate

6E+05 5E-02

7.3142 2-Cyclopenten-1-one, 2-hydroxy- 6E+05 5E-02

21.371 Nonane, 2,2,4,4,6,8,8-heptamethyl- 6E+05 5E-02

10.459 Diethylcyanamide 6E+05 5E-02

24.232 Glycine, N-methyl-N-(4-cyanophenyl)-, methyl ester

6E+05 5E-02

11.787 .alpha.-D-Xylopyranoside, methyl, 2,4-dimethanesulfonate

6E+05 5E-02

31.413 cis-7-Carbomethoxy-2-octenedioic acid, dimethyl ester

6E+05 5E-02

14.012 Phenol, 3,5-dimethyl- 5E+05 5E-02

41

11.109 Cyclohexane, 1-isopropyl-1-methyl- 5E+05 5E-02

23.853 3-Ethyl-2,6,10-trimethylundecane 5E+05 5E-02

14.849 Cyclopentasiloxane, decamethyl- 5E+05 5E-02

14.228 Dimethyl trisulfide 5E+05 5E-02

12.516 2-Piperidinoethyl o-chlorobenzoate 5E+05 5E-02

9.9397 Resorcinol, 2-acetyl- 5E+05 5E-02

22.761 2-Methyl-4-phenyl-butyric acid, methyl ester 5E+05 4E-02

13.924 L-Proline, propyl ester 5E+05 4E-02

17.119 3-Methyl-2-butenoic acid, cyclobutyl ester 5E+05 4E-02

11.28 Benzene, 1-ethyl-4-methyl- 5E+05 4E-02

19 1H-Pyrazole-4-carboxylic acid, 3-amino- 5E+05 4E-02

20.849 (Z)-(Z)-Hex-3-en-1-yl 2-methylbut-2-enoate 5E+05 4E-02

15.954 Ethane, 1,1-dimethoxy- 5E+05 4E-02

41.708 Cyclodecasiloxane, eicosamethyl- 5E+05 4E-02

34.718 Pyrazino[1,2-a]indole-1,4-dione, 2,3-dihydro-2-methyl-3-methylene-

5E+05 4E-02

21.545 Tetradecane, 2,2-dimethyl- 5E+05 4E-02

14.487 Cyclopropane, [(1-propenyloxy)methyl]- 5E+05 4E-02

12.401 1-Hexene, 3-methyl-6-phenyl-4-(1-phenylethoxy)-

5E+05 4E-02

10.19 1H-1,2,4-Triazol-3-amine, 5-methyl- 5E+05 4E-02

10.161 2-Thiophenecarboxylic acid, 4-nitrophenyl ester 5E+05 4E-02

21.847 2'-Hydroxy-4'-methoxyacetophenone, 2-methylpropionate

5E+05 4E-02

39.001 Hexadecanamide 5E+05 4E-02

7.1644 4,6-Octadiyn-3-one, 2-methyl- 5E+05 4E-02

10.432 Sorbic acid vinyl ester 5E+05 4E-02

9.4714 Furan, 2-methoxy- 4E+05 4E-02

19.862 1H-Pyrazole, 4,5-dihydro-3-methyl-1-propyl- 4E+05 4E-02

43.878 Tetracosamethyl-cyclododecasiloxane 4E+05 4E-02

40.129 Benzene, 1,1'-sulfonylbis[4-chloro- 4E+05 4E-02

17.369 Phenol, 2-propyl- 4E+05 4E-02

31.352 1-Naphthalenecarboxylic acid, ethyl ester 4E+05 4E-02

13.759 Isophthalic acid, di(2-isopropylphenyl) ester 4E+05 4E-02

18.59 Pyrrolidine-2,5-dione, 1-(2-furoyl)- 4E+05 4E-02

12.097 Benzeneacetaldehyde 4E+05 4E-02

10.64 Hexane, 3,4-bis(1,1-dimethylethyl)-2,2,5,5-tetramethyl-

4E+05 4E-02

20.991 1-tert-Butyl-N-(2,4-dimethylphenyl)pyrrolidine-2-carboxamide

4E+05 4E-02

6.7786 Propanal, propylhydrazone 4E+05 3E-02

20.093 Heptane, 1,1'-oxybis- 4E+05 3E-02

20.85 Heptylcyclohexane 4E+05 3E-02

20.079 Phenol, 2,3,5-trimethyl- 4E+05 3E-02

7.302 Silanol, trimethyl-, nitrate 4E+05 3E-02

7.4199 Propanal, butylhydrazone 4E+05 3E-02

14.848 Succinic acid, 2-methylpent-3-yl pentafluorophenyl ester

4E+05 3E-02

19.347 Cyclobutyl bromide 4E+05 3E-02

26.984 Diethyl Phthalate 4E+05 3E-02

42

24.494 2',6'-Dihydroxy-3'-methylacetophenone 4E+05 3E-02

22.6 1-Nonylcycloheptane 4E+05 3E-02

22.604 Hexane, 3,4-bis(1,1-dimethylethyl)-2,2,5,5-tetramethyl-

4E+05 3E-02

20.662 Butanamide, N-(4-fluorophenyl)- 4E+05 3E-02

27.264 Nonane, 3-methyl-5-propyl- 4E+05 3E-02

13.876 o-Cymene 4E+05 3E-02

9.3709 1-Octyn-3-ol, 3-methyl- 4E+05 3E-02

11.577 Propanoic acid, anhydride 4E+05 3E-02

23.56 6-Methyl-4-indanol 4E+05 3E-02

27.089 1H-Isoindole, 2,3-dihydro- 4E+05 3E-02

16.38 d-Proline, N-methoxycarbonyl-, dodecyl ester 3E+05 3E-02

20.291 Phenol, TMS derivative 3E+05 3E-02

10.807 Succinic acid, 2,2-dichloroethyl tetrahydrofurfuryl ester

3E+05 3E-02

13.724 2-n-Butyl furan 3E+05 3E-02

12.422 Valeric anhydride 3E+05 3E-02

8.4268 2-Propanamine, N,N'-methanetetraylbis- 3E+05 3E-02

21.21 Decane, 3,3,6-trimethyl- 3E+05 3E-02

18.714 1H-Pyrazole-4-carboxylic acid, 3-amino- 3E+05 3E-02

23.718 2H-1-Benzopyran, 3,4-dihydro-2,2-dimethyl- 3E+05 3E-02

12.699 Ethanone, 1-(1H-pyrrol-2-yl)- 3E+05 3E-02

44.311 Phenol, 2,2'-methylenebis[6-(1,1-dimethylethyl)-4-ethyl-

3E+05 3E-02

17.888 3',5'-Dihydroxyacetophenone 3E+05 3E-02

15.241 Benzene, 4-ethenyl-1,2-dimethyl- 3E+05 3E-02

34.471 1H-Indene, 2,3-dihydro-1-methyl-3-octyl- 3E+05 3E-02

24.803 p-Methoxyheptanophenone 3E+05 3E-02

17.172 Undecane, 6,6-dimethyl- 3E+05 3E-02

29.391 Cyclohexane, tetracosyl- 3E+05 3E-02

17.241 3,4-Dimethoxytoluene 3E+05 3E-02

18.308 Cyclohexanone, 3-(3,3-dimethylbutyl)- 3E+05 3E-02

11.291 Sulfurous acid, di(cyclohexylmethyl) ester 3E+05 3E-02

11.175 Butane, 1-methoxy- 3E+05 3E-02

15.244 2-Fluorobenzoic acid, 1,3-dioxo-1,3-dihydroisoindol-2-yl ester

3E+05 3E-02

37.599 13-Octadecenoic acid, methyl ester 3E+05 3E-02

18.773 Norbornane, 2-isobutyl- 3E+05 3E-02

18.771 Furan, tetrahydro-2-isopentyl-5-propyl- 3E+05 3E-02

16.103 Pentanedioic acid, 2,4-dimethyl-, dimethyl ester 3E+05 3E-02

45.928 2-Thiobarbituric acid, tris(tert-butyldimethylsilyl) deriv.

3E+05 3E-02

45.921 Tetracosamethyl-cyclododecasiloxane 3E+05 3E-02

11.626 2,4,6-Octatriene, 2,6-dimethyl- 3E+05 2E-02

20.89 2,3,5-Trimethyl-2,3,5-hexanetricarbonitrile 3E+05 2E-02

16.921 Pentanedioic acid, 2,4-dimethyl-, dimethyl ester 3E+05 2E-02

14.717 5-Hexen-3-one 3E+05 2E-02

7.7571 2-Butanone, 1,1,1-trifluoro- 3E+05 2E-02

21.246 Cyclohexane, 1,1'-methylenebis- 3E+05 2E-02

16.105 d-Proline, N-methoxycarbonyl-, dodecyl ester 3E+05 2E-02

43

14.984 Benzene, 4-ethenyl-1,2-dimethyl- 3E+05 2E-02

17.384 2,2,3,3,4,4-Hexamethyltetrahydrofuran 3E+05 2E-02

36.558 Etoxeridine 3E+05 2E-02

21.856 Ethanone, 1-(2-hydroxy-4-methoxyphenyl)- 3E+05 2E-02

18.638 Borane, diethyl(decyloxy)- 3E+05 2E-02

10.903 Diethylcyanamide 3E+05 2E-02

23.582 Cyclohexane, octyl- 3E+05 2E-02

36.159 2(1H)-Pyridinone, 6-phenyl- 2E+05 2E-02

37.466 9,15-Octadecadienoic acid, methyl ester, (Z,Z)- 2E+05 2E-02

16.458 4,6-Dimethyloctane-3,5-dione 2E+05 2E-02

21.147 Ethanone, 1-(2-hydroxy-6-methoxyphenyl)- 2E+05 2E-02

12.437 Succinic acid, di(3-phenylprop-2-en-1-yl) ester 2E+05 2E-02

20.814 .alpha.-Oxo-furan-2-acetonitrile 2E+05 2E-02

22.103 Cyclohexane, octyl- 2E+05 2E-02

37.168 5-Benzoylpentanoic acid 2E+05 2E-02

19.956 4-Acetoxy-3-methoxystyrene 2E+05 2E-02

17.56 N-Benzyloxy-2,2-bis(trifluoromethyl)aziridine 2E+05 2E-02

9.6315 Dimethyl trisulfide 2E+05 2E-02

37.467 1H-Imidazole, 2-ethyl- 2E+05 2E-02

7.0971 Diethylcyanamide 2E+05 2E-02

7.0192 Butane, 2,3-dichloro-2-methyl- 2E+05 2E-02

17.853 1-Propanol, dl-2-benzylamino-, 2E+05 2E-02

54.405 Tetracosamethyl-cyclododecasiloxane 2E+05 2E-02

20.988 L-Proline, N-propyl-, propyl ester 2E+05 2E-02

20.564 Sulfurous acid, 2-ethylhexyl hexyl ester 2E+05 2E-02

19.641 Cyclohexasiloxane, dodecamethyl- 2E+05 2E-02

36.391 1-Aminocyclopentanecarboxylic acid, N-isobutoxycarbonyl-, isohexyl ester

2E+05 2E-02

21.346 5-Trimethylsilylpent-2-en-4-yne 2E+05 2E-02

20.245 Decanedioic acid, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester

2E+05 2E-02

6.7427 Imidazol-1-yl-acetic acid, methyl ester 2E+05 2E-02

19.385 Thiophen-2-methylamine, N,N-dibutyl- 2E+05 2E-02

36.876 Pyrazole-3-carboxamide, N-(4-methoxyphenyl)-4-amino-1-methyl-

2E+05 2E-02

14.576 Sulfurous acid, butyl octyl ester 2E+05 2E-02

47.837 Tetracosamethyl-cyclododecasiloxane 2E+05 2E-02

38.096 Methyl stearate 2E+05 2E-02

21.508 N-Formyl(4-hydroxy-2-methoxyphenyl)alanine,ethyl ester

2E+05 2E-02

22.992 Decahydro-1,1,4a,5,6-pentamethylnaphthalene 2E+05 2E-02

44.839 Phthalic acid, di(oct-3-yl) ester 2E+05 2E-02

11.047 1H-Pyrazole, 4,5-dihydro-5-propyl- 2E+05 2E-02

14.942 1-Methyl pyrrolidin-3-amine 2E+05 2E-02

18.39 Alanine, N-methyl-n-propargyloxycarbonyl-, heptyl ester

2E+05 2E-02

6.4403 2-Methylthiolane, S,S-dioxide 2E+05 2E-02

21.362 1,2-Benzenediol, o-(2-bromopropionyl)-o'-(4-ethylbenzoyl)-

2E+05 2E-02

44

15.58 3-Benzoylamino-2-methyl-butyric acid, ethyl ester

2E+05 2E-02

24.121 Tetradecane, 3-methyl- 2E+05 2E-02

21.025 Ethanone, 1-(2-hydroxy-5-methoxyphenyl)- 2E+05 2E-02

12.529 2-Thiopheneacetic acid, 2-tetrahydrofurylmethyl ester

2E+05 2E-02

10.273 Silane, trimethyl(3-methyl-1-butynyl)- 2E+05 2E-02

29.312 Succinic acid, 1,1,1-trifluoroprop-2-yl 2-methylpent-3-yl ester

2E+05 2E-02

17.347 Resorcinol, 2-acetyl- 2E+05 2E-02

15.747 Hexane, 3,4-bis(1,1-dimethylethyl)-2,2,5,5-tetramethyl-

2E+05 2E-02

22.987 2-Amino-m-cresol, N-acetyl- 2E+05 2E-02

19.931 Undecane, 6,6-dimethyl- 2E+05 2E-02

10.558 2H-Pyran-3(4H)-one, 6-ethenyldihydro-2,2,6-trimethyl-

2E+05 2E-02

18.953 Thiophene-2-carboxamide, N-methyl-N-(hept-2-yl)-

2E+05 2E-02

21.072 Propanoic acid, 2,2-dimethyl-, anhydride with diethylborinic acid

2E+05 2E-02

10.717 2-Buten-1-one, 1-(6,7,7-trimethyl-2,3-dioxabicyclo[2.2.2]oct-5-en-1-yl)-, [1R-[1.alpha.(E),4.beta.]]-

2E+05 2E-02

34.468 4-(Fluoromethyl)-5-methyl-2-phenyl-2H-1,2,3-triazole

2E+05 2E-02

20.347 2-Heptanone, 6-(2-furanyl)-6-methyl- 2E+05 1E-02

30.079 D-Norleucine, N-allyloxycarbonyl-, propyl ester 2E+05 1E-02

10.026 4-Hexen-3-one 2E+05 1E-02

17.616 Benzothiazole 2E+05 1E-02

11.092 Ethanone, 1-(2,4-dihydroxyphenyl)- 2E+05 1E-02

25.899 1-Dodecanethiol 2E+05 1E-02

23.976 Cycloheptasiloxane, tetradecamethyl- 2E+05 1E-02

20.999 Ethanone, 1-(4-ethylphenyl)- 2E+05 1E-02

20.432 Furan, 2,5-dibutyl- 2E+05 1E-02

37.368 Benzonitrile, 4-ethenyl- 2E+05 1E-02

38.099 1,3-Dioxolane, 2-methyl-2-tridecyl- 2E+05 1E-02

29.115 Benzamide, 2,5-difluoro-N-isobutyl- 2E+05 1E-02

29.54 Carbonic acid, eicosyl vinyl ester 2E+05 1E-02

25.949 2-Diethylcarbamoyl-1,3-benzodioxole 2E+05 1E-02

24.033 3,6-Dimethyl-4H-furo[3,2-c]pyran-4-one 2E+05 1E-02

36.426 2-Amino-4-phenylpyrimidine 2E+05 1E-02

22.432 2-Thiopheneacetic acid, oct-3-en-2-yl ester 2E+05 1E-02

31.739 1,4-Naphthalenedione, 5,8-dihydroxy-2,3,7-trimethyl-

2E+05 1E-02

34.775 L-Glutamic acid, N-methyl-N-methoxycarbonyl-, dimethyl ester

1E+05 1E-02

17.444 Methanol, TBDMS derivative 1E+05 1E-02

49.626 Tetracosamethyl-cyclododecasiloxane 1E+05 1E-02

11.212 4-Hexen-3-one, 5-methyl- 1E+05 1E-02

18.592 2,5-Cyclohexadiene-1,4-dione, 2-(trimethylsilyl)- 1E+05 1E-02

23.157 1H-Inden-1-one, 2,3-dihydro-3,4,7-trimethyl- 1E+05 1E-02

45

20.906 Benzaldehyde, 4-ethoxy- 1E+05 1E-02

22.562 Thiophene, 2-propyl- 1E+05 1E-02

20.016 1-Adamantanecarboxylic acid, 2-phenylethyl ester

1E+05 1E-02

11.87 2-Octene, 2,3,7-trimethyl- 1E+05 1E-02

12.428 Thiazolidine, 3-methyl- 1E+05 1E-02

38.004 D-Alanine, N-(2,6-difluoro-3-methylbenzoyl)-, undecyl ester

1E+05 1E-02

14.25 Trimethylphosphine oxide 1E+05 1E-02

28.707 Imidazole, 5-carbonylvinyl-4-nitro- 1E+05 1E-02

23.361 Cyclohexanol, 1-(4-fluorophenyl)-4-hexyl- 1E+05 1E-02

15.464 Propanal, dipropylhydrazone 1E+05 1E-02

10.044 Benzeneethanol, .beta.-ethenyl- 1E+05 1E-02

15.13 2,4-Dimethyl-6-oxo-1,6-dihydro-3-pyridinecarbonitrile

1E+05 1E-02

17.646 cis,trans-3-Ethylbicyclo[4.4.0]decane 1E+05 1E-02

37.236 9-Octadecenenitrile, (Z)- 1E+05 1E-02

9.9681 1-Pentanone, 1-(2-thienyl)- 1E+05 1E-02

39.881 4-(N-Methyl-N-methoxy)indancarboxamide 1E+05 1E-02

16.656 Benzene, pentamethyl- 1E+05 1E-02

8.1374 Propanenitrile, 3-(2-methoxy-1-methylethoxy)- 1E+05 1E-02

22.738 Benzene, pentamethyl- 1E+05 1E-02

14.637 Orcinol 1E+05 1E-02

21.107 Ethanone, 1-[4-(1-methylethenyl)phenyl]- 1E+05 1E-02

15.927 2'-Hydroxy-5'-methoxyacetophenone, 2-methylpropionate

1E+05 1E-02

43.384 1,2-Propanediol, 3-benzyloxy-1,2-diacetyl- 1E+05 1E-02

19.125 1H-Inden-1-one, 2,3-dihydro- 1E+05 1E-02

16.945 1,4-Benzenediamine, N,N-dimethyl- 1E+05 1E-02

21.463 1,1'-Bicycloheptyl 1E+05 1E-02

19.737 5-Isopropyl-2-methylphenyl carbanilate 1E+05 1E-02

24.828 2-Pentenoic acid, 5-phenyl-, ethyl ester, (E)- 1E+05 1E-02

24.864 3-Ethyl-3-buten-2-one semicarbazone 1E+05 1E-02

38.614 Nonanamide 1E+05 1E-02

27.019 Sulfonium, (cyanoamino)diphenyl-, hydroxide, inner salt

1E+05 1E-02

19.985 3-Methyl-thiophene-2-carboxamide 1E+05 1E-02

21.873 Thiophene, 2-ethyl-5-heptyl- 1E+05 1E-02

21.198 (E)-2-(4-Methoxyphenyl)ethan-2-one methoxime

1E+05 1E-02

10.472 Tioxolone 1E+05 1E-02

16.101 2,2'-Oxybis(ethane-2,1-diyl) diheptanoate 1E+05 1E-02

36.384 Bicyclo[2.2.2]oct-2-ene, 1,4,5,5,6,6-hexafluoro-2,3-dimethyl-

1E+05 1E-02

19.229 2',4'-Dihydroxy-3'-methylpropiophenone 1E+05 1E-02

40.136 2-Thiophenecarboxylic acid, 4-nitrophenyl ester 1E+05 9E-03

12.137 Benzene, 1,4-diethyl- 1E+05 9E-03

29.575 2-Methylbenzylamine, N,N-diheptyl- 1E+05 9E-03

13.812 4-Methylbicyclo(3.2.2)nona-3,6-dien-2-one 1E+05 9E-03

8.5673 2-(Butyliden-2-one)tetrahydrofuran 1E+05 9E-03

46

34.884 L-Glutamic acid, N-methyl-N-methoxycarbonyl-, dimethyl ester

1E+05 9E-03

7.3942 2,3-Benzofurandione 1E+05 9E-03

29.786 2-Furoic acid, 4-methoxyphenyl ester 1E+05 9E-03

13.983 Norbornane, 2-isobutyl- 1E+05 9E-03

18.076 benzamide, N-[4-(2-oxo-2H-1-benzopyran-3-yl)phenyl]-

1E+05 9E-03

11.43 Benzene, 1-ethyl-2,4-dimethyl- 1E+05 9E-03

16.743 4-Chlorobutyric acid, 4-isopropylphenyl ester 1E+05 9E-03

14.932 Aminothiazole 1E+05 9E-03

37.054 1,1'-Biphenyl, 6-hydroxy-2',3',4'-trimethoxy- 1E+05 8E-03

17.626 2-Heptenoic acid, 4-nitrophenyl ester 1E+05 8E-03

16.241 1,4 Benzodioxan-6-amine 1E+05 8E-03

52.804 Hexanedioic acid, 3,4-bis(ethoxycarbonyl)-2,5-dioxo-, diethyl ester

9E+04 8E-03

19.594 3',5'-Dihydroxyacetophenone 9E+04 8E-03

22.255 1,1,1,5,5,5-Hexafluoropentan-3-one 9E+04 8E-03

49.676 N-1-Adamantyl-4-pyridinecarboxaldimine 9E+04 8E-03

17.158 Glycine, N-trifluoroacetyl-, isopropyl ester 9E+04 8E-03

20.588 Methyl 2-methyl-3-phenyl-prop-2-enoate 9E+04 8E-03

27.596 Benzene, 1,2,3-trimethyl- 9E+04 8E-03

23.158 1H-Benzimidazole, 2-(1,1-dimethylethyl)- 9E+04 8E-03

15.001 Benzene, pentamethyl- 9E+04 8E-03

31.817 1-Benzoyl-2-t-butyl-5-methyl-5-(2-methylthioethyl)imidazolidin-4-one

9E+04 8E-03

41.703 Cholest-2-eno[2,3-b]indole, 1'-methyl-5'-methoxy-

9E+04 8E-03

20.733 2'-Hydroxy-4'-methoxyacetophenone, acetate 9E+04 8E-03

51.307 Tetracosamethyl-cyclododecasiloxane 9E+04 8E-03

14.032 Thiophene, 2-propyl- 9E+04 8E-03

52.893 Tetracosamethyl-cyclododecasiloxane 9E+04 8E-03

30.186 Benzene, (1-butyloctyl)- 9E+04 8E-03

20.389 Isovaleric acid, 3-methylbutyl-2 ester 9E+04 8E-03

23.649 Valeric acid, 4-nitrophenyl ester 9E+04 8E-03

21.618 Benzamide, 4-fluoro-N-methallyl- 9E+04 8E-03

24.228 1-Methoxy-4-(2'-nitro-2'propenyl)benzene 9E+04 8E-03

25.017 Pentanoic acid, 5-hydroxy-, 2,4-di-t-butylphenyl esters

9E+04 8E-03

18.822 3-Ethoxythiophenol, S-acetyl- 9E+04 8E-03

20.209 Acetoisovanillone, trimethylacetate 9E+04 8E-03

17.96 Cyclohexane, hexyl- 9E+04 7E-03

9.7019 Heptane, 4-ethyl-2,2,6,6-tetramethyl- 9E+04 7E-03

18.171 Methylphosphonic acid, di(2-methylpropyl) ester

8E+04 7E-03

42.225 Diboroxane, triethyl[2-(pyridyl)amino]- 8E+04 7E-03

17.728 2,4'-Dimethoxy-2'(tert.-butyldimethylsilyl)oxychalcone

8E+04 7E-03

22.842 2-Isopropenyl-3,6-dimethylpyrazine 8E+04 7E-03

52.883 1-[2,4-Bis(trimethylsiloxy)phenyl]-2-[(4-trimethylsiloxy)phenyl]propan-1-one

8E+04 7E-03

39.39 Ethane, iodo- 8E+04 7E-03

47

32.611 Anthrone, 10-bromo- 8E+04 7E-03

18.067 Hexanedioic acid, ethyl methyl ester 8E+04 7E-03

29.526 Xanthene, 9,9-dimethyl- 8E+04 7E-03

28.456 Benzamide, N-propyl- 8E+04 7E-03

26.391 Nonaneperoxoic acid, 1,1-dimethylethyl ester 8E+04 7E-03

27.971 Benzene, (1-butylheptyl)- 7E+04 6E-03

37.027 Naphtho[2,3-c]furan-1(3H)-one, 6-hydroxy-5,7-dimethoxy-

7E+04 6E-03

22.687 1-Bromo-3-butene-2-ol 7E+04 6E-03

20.498 2,4-Dimethylpentan-3-yl 2-methylbutanoate 7E+04 6E-03

14.088 1,3-Benzenediol, o-(4-methylbenzoyl)-o'-(2-methoxybenzoyl)-

7E+04 6E-03

24.022 2-Isopropylamino-4-methylbenzonitrile 7E+04 6E-03

37.404 Ethanone, 2,2,2-trifluoro-1-phenyl- 7E+04 6E-03

36.82 4,8-Dimethyl-2-hydroxyquinoline, tert-butyldimethylsilyl ether

7E+04 6E-03

19.494 Di-trimethylsilyl peroxide 7E+04 6E-03

38.286 Naphtho[2,3-c]furan-1(3H)-one, 6-hydroxy-5,7-dimethoxy-

7E+04 6E-03

15.548 2H-Inden-2-one, 1,3-dihydro- 7E+04 6E-03

38.876 Naphtho[2,3-c]furan-1(3H)-one, 6-hydroxy-5,7-dimethoxy-

7E+04 6E-03

35.485 Pyrazole-3-carboxamide, N-(4-methoxyphenyl)-4-amino-1-methyl-

7E+04 6E-03

43.883 2-Thiobarbituric acid, tris(tert-butyldimethylsilyl) deriv.

7E+04 6E-03

25.48 4-Methoxyphenylacetic acid ethyl ester 7E+04 6E-03

17.012 2-Pyrazoline, 1-isopropyl-3,4-dimethyl- 7E+04 6E-03

25.303 4,4'-Bis(dimethylamino)terephthalanilide 7E+04 6E-03

25.388 5,6-Dimethyl-1H-1,3-benzodiazole-2-carbaldehyde

7E+04 6E-03

23.794 L-Proline, N-(hexanoyl)-, decyl ester 7E+04 6E-03

33.78 2H,8H-Benzo[1,2-b:5,4-b']dipyran-2-one, 8,8-dimethyl-

7E+04 6E-03

23.124 2-Isopropenyl-3,6-dimethylpyrazine 6E+04 6E-03

14.711 8-Oxabicyclo[3.2.1]oct-6-en-3-one, 2,4-dimethyl- 6E+04 6E-03

38.396 D-Alanine, N-(2,6-difluoro-3-methylbenzoyl)-, pentadecyl ester

6E+04 5E-03

16.686 9H-Fluorene, 9-methyl- 6E+04 5E-03

44.686 Triphenylphosphine oxide 6E+04 5E-03

42.174 Isophthalic acid, 2,6-dichlorophenyl hexyl ester 6E+04 5E-03

6.3968 Propane, 1,3-dimethoxy- 6E+04 5E-03

24.328 3,5-Heptanedione, 4-ethyl-2,2,6,6-tetramethyl- 6E+04 5E-03

31.536 2',3',4',5',6'-Pentafluoroacetophenone 6E+04 5E-03

33.658 2H,8H-Benzo[1,2-b:5,4-b']dipyran-2-one, 8,8-dimethyl-

6E+04 5E-03

49.302 N-Ethyl-5-methyl-5-undecanamine 6E+04 5E-03

31.494 2-Propanol, 1-chloro-, phosphate (3:1) 6E+04 5E-03

16.803 Propanoic acid, 2-(3-cyano-4-ethyl-5-methyl-2-thienylamino)-3,3,3-trifluoro-2-(dimethylaminocarbonylamino)-, ethyl ester

6E+04 5E-03

48

33.267 Isoparvifuran 5E+04 5E-03

24.256 l-Phenylalanine, N-(2-thienylcarbonyl)-, methyl ester

5E+04 5E-03

22.08 2,5,6-Trimethylbenzimidazole 5E+04 5E-03

26.349 6-Phenyl-2-hexenyl vinyl ether 5E+04 5E-03

23.208 Methyl 2-methyl-3-phenyl-prop-2-enoate 5E+04 5E-03

12.023 1,3-Dioxepane, 5-methyl-2-pentadecyl- 5E+04 5E-03

9.9597 Ethane, pentachloro- 5E+04 4E-03

19.723 Ethene, iodo- 5E+04 4E-03

37.826 Pyridine-4-carboxamide, N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-

5E+04 4E-03

30.467 1-Benzylimidazolidine-2,4,5-trione 5E+04 4E-03

19.244 2-Cyclohexen-3-ol-1-one, 2-[1-iminoethyl]- 5E+04 4E-03

27.379 2,3,4-Trifluorobenzoic acid, 3-phenylpropyl ester 5E+04 4E-03

44.495 Isobutyl 3-(5-amino-1,3,4-thiadiazol-2-yl)propionate

5E+04 4E-03

18.101 Silane, diethyl(2-ethoxyethyloxy)octadecyloxy- 5E+04 4E-03

37.587 2-(4-Fluoro-phenylthio)indan 5E+04 4E-03

21.93 Benzoic acid, 4-hydroxy-, 2-hydroxypropyl ester 5E+04 4E-03

22.915 3-ethoxy-4-hydroxybenzonitrile 4E+04 4E-03

6.4766 Trimethylphosphine oxide 4E+04 4E-03

49.709 1,2-Benzenediol, o-isonicotinoyl-o'-valeryl- 4E+04 4E-03

25.629 3,4-Dihydro-2,7-dimethylpyrimido[4,5-d]pyrimidine

4E+04 4E-03

28.208 Benzene, (1-propyloctyl)- 4E+04 4E-03

40.097 6-Hepten-2-one, 7-phenyl- 4E+04 4E-03

19.326 1-Phenyldodec-1-en-3-one 4E+04 3E-03

39.465 Pyridine-4-carboxamide, N-methyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-

4E+04 3E-03

15.397 (1H)Pyrrole-3-carbonitrile, 2-methyl- 4E+04 3E-03

22.984 2',4'-Dihydroxy-3'-methylpropiophenone 4E+04 3E-03

17.825 Silane, (4-methoxyphenyl)trimethyl- 4E+04 3E-03

19.037 Boron, (hexahydro-2H-azepin-2-onato-N1,O2)bis(1-methylethyl)-, (t-4)-

4E+04 3E-03

9.386 1,4-Cyclohexanedione 4E+04 3E-03

24.584 7-Amino-4-methyl-2-quinolinol 4E+04 3E-03

37.154 Xanthen-9-one, 1,8-dihydroxy-3,5-dimethoxy- 3E+04 3E-03

25.693 Silane, diethyloctadecyloxy(2-methoxyethoxy)- 3E+04 3E-03

34.71 Valine, N-methyl-N-methoxycarbonyl-, nonyl ester

3E+04 3E-03

42.201 Succinic acid, butyl 3-hexyl ester 3E+04 3E-03

29.694 4-tert-Butylphthalonitrile 3E+04 3E-03

24.925 2H-1-Benzopyran, 6,7-dimethoxy-2,2-dimethyl- 3E+04 3E-03

16.991 Benzene, pentamethyl- 3E+04 3E-03

44.042 L-Glutamic acid, N-methyl-N-methoxycarbonyl-, dimethyl ester

3E+04 3E-03

24.736 2,3,4-Trifluorobenzoic acid, 3-phenylpropyl ester 3E+04 3E-03

23.426 Ethanone, 1-(2,3,4-trihydroxyphenyl)- 3E+04 3E-03

21.38 Silane, diethyloctadecyloxy(2-methoxyethoxy)- 3E+04 3E-03

49

37.384 Benzoic acid, 2-[[(4-bromophenyl)imino]phenylmethoxy]-5-chloro-, methyl ester

3E+04 3E-03

30.826 1,2-Oxaphosphole, 3,5-bis(1,1-dimethylethyl)-2,5-dihydro-2-hydroxy-, 2-oxide

3E+04 3E-03

36.7 Benzene, 1-chloro-3-(phenylethynyl)- 3E+04 3E-03

15.807 Benzene, pentamethyl- 3E+04 3E-03

22.675 Naphtho[2,1-b]furan 3E+04 3E-03

27.829 Propionic acid, 3-benzoylamino-3-(4-tert-butylphenyl)-

3E+04 2E-03

27.762 2-Quinolinecarboxylic acid, methyl ester 3E+04 2E-03

37.758 L-Glutamic acid, N-methyl-N-methoxycarbonyl-, dimethyl ester

3E+04 2E-03

25.228 (E)-Stilbene 3E+04 2E-03

41.654 L-Glutamic acid, N-methyl-N-methoxycarbonyl-, dimethyl ester

3E+04 2E-03

25.161 Aminoformic acid, N-n-hexyl-, 2,6-diisopropylphenyl(ester)

3E+04 2E-03

32.245 2-Trimethylsilyl-3-trimethylsilylamino-1,2,4-triazole

2E+04 2E-03

17.236 1-Butanamine, N-(2-pyridinylmethylene)- 2E+04 2E-03

51.905 2-Furanmethanamine, tetrahydro-N-[[2-(trifluoromethyl)phenyl]methyl]-

2E+04 2E-03

33.131 Isoparvifuran 2E+04 2E-03

33.164 Benzenealdehyde, 2-bromo-5-hydroxy-4-methoxy-

2E+04 2E-03

31.267 Dibenz[b,f]][1,4]oxazepine 2E+04 2E-03

28.139 3-Allyl-2-methyl-4(3H)-quinazolinethione 2E+04 2E-03

54.775 5-(3-tert-Butylamino-6-methylimidazo[1,2-a]pyridin-2-yl)-2-methoxyphenol

2E+04 1E-03

48.96 [1,2,5]Oxadiazolo[3,4-E]bis[1,2,4]triazolo[4,3-a:3',4'-c]pyrazine, 5,10-dimethyl-

2E+04 1E-03

38.743 7,15-Dihydroxydehydroabietic acid, methyl ester,di(trimethylsilyl)ether

1E+04 1E-03

25.408 2-Amino-3,4:5,6-bis(trimethylene)pyridine 1E+04 1E-03

40.548 1-Phenyl-3-formylpyrazolo[3,4-b]quinoxaline 1E+04 1E-03

23.93 l-Phenylalanine, N-(2,3,4-trifluorobenzoyl)-, methyl ester

1E+04 9E-04

53.184 Pentafluoropropionamide, N-benzyl-N-dodecyl- 1E+04 8E-04

20.159 1H-Benzimidazole, 1-ethyl- 9E+03 8E-04

52.813 Cholesteryl laurate 9E+03 8E-04

40.963 thiazolo[4,5-c]pyridin-2-amine, N-phenyl- 7E+03 6E-04

Table 19 - Sample 1L0 GC-MS spectra – ordered from the highest component area to the lowest

Component RT Compound Name Match Factor Component Area

13.061 Phenol, 2-methoxy- 99.068 2E+08

21.95 Vanillin 99.042 9E+07

24.123 Ethanone, 1-(3-hydroxy-4-

methoxyphenyl)-

98.784 2E+07

50

30.894 Phenanthrene-D10 96.119 9E+06

25.141 Guaiacol, 4-butyl- 94.282 6E+06

6.1961 N-Ethyl-2-

isopropoxycarbonylazetidine

76.508 2E+06

9.6913 Phenol 98.146 3E+06

16.172 2-Methoxy-5-methylphenol 98.228 3E+06

20.622 Phenol, 2,6-dimethoxy- 96.152 3E+06

12.708 p-Cresol 92.83 2E+06

14.88 Benzene, 1,2-dimethoxy- 93.782 2E+06

29.867 5'-Hydroxy-2',3',4'-

trimethylacetophenone

77.076 2E+06

18.605 Phenol, 4-ethyl-2-methoxy- 88.407 9E+05

9.8117 Cyclotetrasiloxane,

octamethyl-

81.219 5E+05

10.386 1,3-Benzodioxole 81.79 4E+05

20.992 Benzaldehyde, 4-hydroxy- 85.194 4E+05

7.8256 Ethane, 1,1,2,2-tetrachloro- 84.959 4E+05

7.6277 Cyclopentane, 1,2,3,4,5-

pentamethyl-

87.56 7E+05

26.481 1-Propanone, 1-(4-hydroxy-3-

methoxyphenyl)-

82.566 2E+05

8.5562 Pyrrolidine 78.424 4E+05

27.947 Homovanillic acid 83.938 4E+05

28.196 Benzaldehyde, 4-hydroxy-3,5-

dimethoxy-

75.639 3E+05

23.4 Phenol, 2-methoxy-4-propyl- 79.317 2E+05

7.3333 2-Cyclopenten-1-one, 2-

methyl-

85.58 3E+05

24.592 benzoic acid, 4-hydroxy-3-

propyl-

64.185 1E+05

15.78 2-Methoxy-5-methylphenol 77.36 1E+05

9.3111 3-Hexyne, 2-methyl- 85.199 2E+05

20.39 Piperonal 80.188 1E+05

9.7376 Azetidine, 3-methyl-3-phenyl- 91.026 3E+05

8.1262 Trimethyldifluorophosphorane 60.52 3E+05

8.5968 Cyclohexane, 1-ethyl-1-

methyl-

67.104 2E+05

7.7089 Sulfurous acid,

cyclohexylmethyl isobutyl

ester

68.91 2E+05

19.639 4-Acetoxy-3-methoxystyrene 81.253 1E+05

17.265 m-Guaiacol 66.916 1E+05

51

8.7787 2,4,4-Trimethyl-1-hexene 63.972 1E+05

6.5191 E-4-Methoxy-2-hexene 67.374 2E+05

13.36 2-Pyrrolidinecarboxylic acid,

1,2-dimethyl-5-oxo-, methyl

ester

70.789 1E+05

24.305 Propane, 2-iodo- 76.006 7E+04

12.036 1,2-Ethanediol, 1,2-diphenyl-,

[R-(R*,R*)]-

75.068 1E+05

28.346 Pyrazole, 5-(4-

methoxyphenyl)-

72.314 8E+04

13.209 1H-Pyrazole, 5-methoxy-1,3-

dimethyl-

67.824 1E+05

26.258 4-(1-Hydroxyallyl)-2-

methoxyphenol

60.962 1E+05

23.974 6-Methoxy-3-

methylbenzofuran

67.712 8E+04

22.706 3-Acetyl-2,5-

dimethylthiophene

65.984 8E+04

14.574 Cyclopentasiloxane,

decamethyl-

88.598 9E+04

13.477 Piperidine, 1-ethyl-2-methyl- 66.968 3E+04

8.3308 2-Cyclopenten-1-one, 3,4-

dimethyl-

69.401 7E+04

Table 20 – 1L1 results ordered from highest component area to lowest component area

Component RT Compound Name Component Area

13.062 Phenol, 2-methoxy- 2E+08

21.95 Vanillin 1E+08

24.123 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)-

3E+07

25.141 Guaiacol, 4-butyl- 1E+07

6.1903 Methane-d, trichloro- 3E+06

9.688 Phenol 3E+06

20.622 Phenol, 2,6-dimethoxy- 4E+06

16.17 2-Methoxy-5-methylphenol 3E+06

29.866 5'-Hydroxy-2',3',4'-trimethylacetophenone

3E+06

30.894 Phenanthrene-D10 1E+06

12.708 p-Cresol 1E+06

18.608 Phenol, 4-ethyl-2-methoxy- 8E+05

27.947 Homovanillic acid 8E+05

26.476 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)-

3E+05

14.884 Benzene, 1,2-dimethoxy- 6E+05

9.8186 Cyclotetrasiloxane, octamethyl- 4E+05

20.995 Benzaldehyde, 4-hydroxy- 5E+05

52

10.387 1,3-Benzodioxole 4E+05

7.631 Cyclopentane, 1,2,3,4,5-pentamethyl- 7E+05

28.196 Benzaldehyde, 4-hydroxy-3,5-dimethoxy-

5E+05

8.5568 Octane, 3-methyl-6-methylene- 4E+05

7.8271 Ethane, 1,1,2,2-tetrachloro- 4E+05

7.329 2-Cyclopenten-1-one, 2-methyl- 3E+05

29.799 4,5-Dimethoxy-2-hydroxyacetophenone

2E+05

23.043 Acetophenone, 4'-hydroxy- 2E+05

23.241 Phenol, 4-pentyl- 2E+05

9.2963 3-Hexyne, 2-methyl- 2E+05

20.385 Piperonal 2E+05

24.595 2',4'-Dihydroxy-3'-methylpropiophenone

1E+05

9.7341 Azetidine, 3-methyl-3-phenyl- 3E+05

25.568 Dimethyl-(isopropyl)-silyloxybenzene 1E+05

24.31 Propane, 2-iodo- 1E+05

7.7116 2,4,4-Trimethyl-1-pentanol, trifluoroacetate

2E+05

19.638 4-Acetoxy-3-methoxystyrene 2E+05

26.259 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)-

2E+05

15.778 Benzene, 1,4-dimethoxy- 1E+05

8.1322 2,5-Hexanedione 2E+05

17.263 m-Guaiacol 1E+05

28.348 7-Methoxy-8-aminoisoquinoline 1E+05

12.037 Carbamic acid, methyl-, 3-methylphenyl ester

2E+05

23.978 6-Methoxy-3-methylbenzofuran 9E+04

13.469 Phosphoric acid, diundecyl methyl ester

6E+04

Table 21 - Sample 1L2 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.073 Phenol, 2-methoxy- 2E+08

21.96 Vanillin 1E+08

24.13 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 4E+07

25.146 Guaiacol, 4-butyl- 2E+07

9.6864 Phenol 5E+06

20.621 Phenol, 2,6-dimethoxy- 9E+06

16.169 2-Methoxy-5-methylphenol 6E+06

6.167 Methane-d, trichloro- 2E+06

29.869 5'-Hydroxy-2',3',4'-trimethylacetophenone 5E+06

27.958 Benzenepropanol, 4-hydroxy-3-methoxy- 4E+06

18.607 Phenol, 4-ethyl-2-methoxy- 2E+06

30.895 Phenanthrene-D10 1E+06

26.479 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)-

8E+05

12.714 p-Cresol 1E+06

53

28.198 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 1E+06

21 Benzaldehyde, 4-hydroxy- 9E+05

14.882 Benzene, 1,2-dimethoxy- 1E+06

29.802 4,5-Dimethoxy-2-hydroxyacetophenone 5E+05

7.6319 Cyclopentane, 1,2,3,4,5-pentamethyl- 7E+05

23.247 Phenol, 4-pentyl- 4E+05

7.3249 2-Cyclopenten-1-one, 2-methyl- 5E+05

10.38 1,3-Benzodioxole 5E+05

23.032 Acetophenone, 4'-hydroxy- 3E+05

9.8184 Cyclotetrasiloxane, octamethyl- 2E+05

9.2694 2-Cyclopenten-1-one, 3-methyl- 5E+05

25.565 Dimethyl-(isopropyl)-silyloxybenzene 4E+05

8.5523 Pyrrolidine 3E+05

7.8247 Ethane, 1,1,2,2-tetrachloro- 3E+05

23.399 Phenol, 2-methoxy-4-propyl- 2E+05

13.208 Ethanone, 1-(2-thienyl)- 2E+05

26.26 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)-

3E+05

20.385 Piperonal 2E+05

24.308 Propane, 2-iodo- 2E+05

17.259 m-Guaiacol 2E+05

8.117 2,5-Hexanedione 2E+05

19.639 Ethanone, 1-(2-hydroxy-5-methylphenyl)- 2E+05

28.346 2-naphthalenol, 6-methoxy- 2E+05

8.8868 2(3H)-Furanone, dihydro-5-methyl- 2E+05

9.7335 Azetidine, 3-methyl-3-phenyl- 3E+05

12.036 Phenol, 2-methyl- 2E+05

11.483 Furan, 2,3,5-trimethyl- 2E+05

8.5998 Sulfurous acid, di(cyclohexylmethyl) ester 2E+05

23.975 6-Methoxy-3-methylbenzofuran 2E+05

7.7058 2,4,4-Trimethyl-1-pentanol, trifluoroacetate 2E+05

30.551 Desaspidinol 8E+04

10.116 Ethanone, 1-(2-furanyl)- 1E+05

52.533 Dodecane, 1-iodo- 4E+04

53.793 Decane, 3,8-dimethyl- 8E+04

29.654 Sebacic acid, ethyl 4-(2-phenylpropyl-2)-phenyl ester

3E+04

Table 22 - Sample 1L3 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.073 Phenol, 2-methoxy- 2E+08

21.958 Vanillin 1E+08

24.131 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 4E+07

25.144 Guaiacol, 4-butyl- 2E+07

9.687 Phenol 6E+06

20.621 Phenol, 2,6-dimethoxy- 1E+07

27.959 Benzenepropanol, 4-hydroxy-3-methoxy- 6E+06

13.053 Fomepizole 4E+06

16.168 2-Methoxy-5-methylphenol 7E+06

54

29.867 5'-Hydroxy-2',3',4'-trimethylacetophenone 6E+06

6.1905 Methane-d, trichloro- 2E+06

18.604 Phenol, 4-ethyl-2-methoxy- 2E+06

26.478 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 1E+06

30.896 Phenanthrene-D10 1E+06

20.996 Benzaldehyde, 4-hydroxy- 1E+06

28.198 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 1E+06

12.714 p-Cresol 1E+06

23.244 Phenol, 4-pentyl- 7E+05

29.8 4,5-Dimethoxy-2-hydroxyacetophenone 6E+05

14.881 Benzene, 1,2-dimethoxy- 1E+06

23.034 Acetophenone, 4'-hydroxy- 4E+05

9.2695 4-Methyl-2H-pyran 6E+05

7.321 2-Cyclopenten-1-one, 2-methyl- 6E+05

7.6295 Cyclopentane, 1,2,3,4,5-pentamethyl- 7E+05

10.376 Succinic acid, 3-chlorophenyl 4-methoxybenzyl ester

6E+05

25.565 Dimethyl-(isopropyl)-silyloxybenzene 4E+05

9.8223 Cyclotetrasiloxane, octamethyl- 2E+05

21.027 2',4'-Dihydroxypropiophenone 4E+05

8.5533 Pyrrolidine 3E+05

13.209 Ethanone, 1-(2-thienyl)- 3E+05

23.406 Phenol, 2-methoxy-4-propyl- 2E+05

15.781 2-Methoxy-5-methylphenol 3E+05

7.8255 Ethane, 1,1,2,2-tetrachloro- 3E+05

17.255 m-Guaiacol 2E+05

24.301 Propane, 2-iodo- 3E+05

8.1082 2,5-Hexanedione 3E+05

26.26 4-(1-Hydroxyallyl)-2-methoxyphenol 4E+05

19.64 Ethanone, 1-(2-hydroxy-5-methylphenyl)- 3E+05

20.386 Piperonal 2E+05

28.347 7-Methoxy-1-naphthol 2E+05

8.8866 2-Azidopropane 2E+05

11.478 Furan, 2,3,5-trimethyl- 2E+05

30.549 Desaspidinol 9E+04

12.029 Phenol, 2-methyl- 2E+05

9.7326 Azetidine, 3-methyl-3-phenyl- 3E+05

31.568 Methanimidamide, N'-(3-methoxyphenyl)-N,N-dimethyl-

2E+05

8.6011 Sulfurous acid, di(cyclohexylmethyl) ester 2E+05

23.974 6-Methoxy-3-methylbenzofuran 2E+05

7.696 Diethylcyanamide 2E+05

27.374 2,3,5,6-Tetrafluoroanisole 2E+05

22.704 3-Acetyl-2,5-dimethylthiophene 1E+05

10.115 Ethanone, 1-(2-furanyl)- 2E+05

14.612 Cyclopentasiloxane, decamethyl- 2E+05

13.477 Phosphoric acid, diundecyl methyl ester 1E+05

8.3381 2-Cyclopenten-1-one, 3,4-dimethyl- 6E+04

55

37.492 1H-isoindole-1,3(2H)-dione, 2-(5-methoxy-8-nitro-1-naphthalenyl)-

9E+03

Table 23 - Sample 1L4 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.05 Phenol, 2-methoxy- 1E+08

21.933 Vanillin 6E+07

24.118 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 2E+07

25.139 Guaiacol, 4-butyl- 9E+06

9.6862 Phenol 3E+06

20.62 Phenol, 2,6-dimethoxy- 3E+06

6.174 4H-1,2,4-Triazol-4-amine 1E+06

16.17 2-Methoxy-5-methylphenol 2E+06

27.947 Benzenepropanol, 4-hydroxy-3-methoxy- 2E+06

29.866 5'-Hydroxy-2',3',4'-trimethylacetophenone 2E+06

18.605 Phenol, 4-ethyl-2-methoxy- 7E+05

9.8142 Cyclotetrasiloxane, octamethyl- 6E+05

12.705 p-Cresol 5E+05

20.987 Benzaldehyde, 4-hydroxy- 5E+05

7.6313 1-Propene, 3-(ethenyloxy)- 7E+05

26.476 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 2E+05

10.39 1,3-Benzodioxole 3E+05

28.193 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 2E+05

30.895 Phenanthrene-D10 3E+05

8.5517 Methacrolein 4E+05

23.242 Phenol, 4-pentyl- 2E+05

23.032 Acetophenone, 4'-hydroxy- 2E+05

7.823 Ethane, 1,1,2,2-tetrachloro- 3E+05

14.885 Benzene, 1,2-dimethoxy- 3E+05

7.3312 2-Cyclopenten-1-one, 2-methyl- 2E+05

9.2991 4-Methyl-2H-pyran 3E+05

29.799 4,5-Dimethoxy-2-hydroxyacetophenone 1E+05

13.197 1-Pentanone, 1-(2-thienyl)- 1E+05

8.1363 2,5-Hexanedione 2E+05

25.565 Dimethyl-(isopropyl)-silyloxybenzene 1E+05

9.7294 .alpha.-Methylstyrene 3E+05

20.386 Piperonal 1E+05

19.642 Ethanone, 1-(2-hydroxy-5-methylphenyl)- 2E+05

7.7095 2,4,4-Trimethyl-1-pentanol, trifluoroacetate 2E+05

26.255 Guaiacol, 4-butyl- 1E+05

17.264 m-Guaiacol 1E+05

13.482 2,4-Dihydroxybenzaldehyde, 2TMS derivative 2E+05

8.9073 Furan, tetrahydro-2,5-dimethyl-, trans-(.+/-.)- 1E+05

24.3 2,4,6,(1H,3H,5H)-Pyrimidinetrione, 5-acetyl- 8E+04

23.969 6-Methoxy-3-methylbenzofuran 9E+04

28.341 7-Methoxy-8-aminoisoquinoline 7E+04

14.581 Cyclopentasiloxane, decamethyl- 7E+04

14.436 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone

4E+04

56

Table 24 - Sample 2L0 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.048 Phenol, 2-methoxy- 1E+08

21.949 Vanillin 1E+08

24.121 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 3E+07

25.138 Guaiacol, 4-butyl- 1E+07

6.1941 Methylene chloride 2E+06

20.618 Phenol, 2,6-dimethoxy- 4E+06

9.684 Phenol 2E+06

29.864 5'-Hydroxy-2',3',4'-trimethylacetophenone 4E+06

16.167 2-Methoxy-5-methylphenol 3E+06

27.949 Benzenepropanol, 4-hydroxy-3-methoxy- 2E+06

30.894 Phenanthrene-D10 1E+06

18.604 Phenol, 4-ethyl-2-methoxy- 1E+06

26.479 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 5E+05

28.193 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 7E+05

20.992 Benzaldehyde, 4-hydroxy- 6E+05

12.703 p-Cresol 7E+05

9.809 Cyclotetrasiloxane, octamethyl- 5E+05

23.4 Phenol, 2-methoxy-4-propyl- 4E+05

24.589 2',4'-Dihydroxy-3'-methylpropiophenone 3E+05

7.6243 Cyclopentane, 1,2,3,4,5-pentamethyl- 7E+05

7.8186 Ethane, 1,1,2,2-tetrachloro- 4E+05

29.796 4,5-Dimethoxy-2-hydroxyacetophenone 3E+05

8.5466 Pyrrolidine 4E+05

23.245 Phenol, 4-pentyl- 3E+05

10.392 1,3-Benzodioxole 3E+05

23.033 Acetophenone, 4'-hydroxy- 2E+05

7.3251 2-Cyclopenten-1-one, 2-methyl- 3E+05

8.1215 2,5-Hexanedione 2E+05

20.383 Piperonal 2E+05

9.7289 .alpha.-Methylstyrene 3E+05

24.421 l-Alanine, N-(2-fluorobenzoyl)-, decyl ester 1E+05

26.26 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 3E+05

9.2965 4-Methyl-2H-pyran 2E+05

19.638 4-Hydroxy-2-methylacetophenone 2E+05

28.346 Pyrazole, 5-(4-methoxyphenyl)- 2E+05

17.262 m-Guaiacol 2E+05

7.7059 2-Acetonylcyclopentanone 2E+05

12.458 Acetophenone 1E+05

14.882 Benzene, 1,2-dimethoxy- 1E+05

31.558 7-Isoquinolinol, 1,2,3,4-tetrahydro-6-methoxy-1-salicyl-

1E+05

24.296 Propane, 2-iodo- 1E+05

29.767 Benzo[d,E]isocoumarin, 3,3-dimethyl- 1E+05

23.97 6-Methoxy-3-methylbenzofuran 1E+05

22.71 Phenol, 2,6-dimethoxy-, acetate 1E+05

8.9139 2,5-Hexanediol 9E+04

57

29.656 2,6-Diisopropylnaphthalene 1E+05

12.039 Carbamic acid, methyl-, 3-methylphenyl ester 1E+05

13.467 2,4-Dihydroxybenzaldehyde, 2TMS derivative 9E+04

11.264 2-(2-Propen-1-ylidene)aminoacetonitrile 1E+05

28.654 2,6-Diisopropylnaphthalene 6E+04

14.573 Cyclopentasiloxane, decamethyl- 7E+04

29.54 Benzo[d,E]isocoumarin, 3,3-dimethyl- 5E+04

28.484 2,6-Diisopropylnaphthalene 5E+04

Table 25 - sample 2L1 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.054 Phenol, 2-methoxy- 2E+08

21.945 Vanillin 9E+07

24.122 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 3E+07

25.139 Guaiacol, 4-butyl- 1E+07

6.2269 Methylene chloride 9E+06

20.62 Phenol, 2,6-dimethoxy- 4E+06

29.864 5'-Hydroxy-2',3',4'-trimethylacetophenone 3E+06

16.17 2-Methoxy-5-methylphenol 3E+06

27.95 Benzenepropanol, 4-hydroxy-3-methoxy- 3E+06

9.6949 Phenol 3E+06

18.606 Phenol, 4-ethyl-2-methoxy- 1E+06

7.6304 Cyclopentane, 1,2,3,4,5-pentamethyl- 8E+05

20.991 Benzaldehyde, 4-hydroxy- 8E+05

12.705 p-Cresol 6E+05

28.197 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 6E+05

9.819 Cyclotetrasiloxane, octamethyl- 5E+05

6.5234 2-Hexene, 2-methoxy- 5E+05

30.896 Phenanthrene-D10 5E+05

26.479 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 5E+05

8.554 Octane, 3-methyl-6-methylene- 5E+05

23.243 Phenol, 4-pentyl- 4E+05

7.8248 Ethane, 1,1,2,2-tetrachloro- 4E+05

10.39 1,3-Benzodioxole 3E+05

9.7343 Azetidine, 3-methyl-3-phenyl- 3E+05

29.799 4,5-Dimethoxy-2-hydroxyacetophenone 3E+05

26.256 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 3E+05

8.7548 Phenyl-pentamethyl-disiloxane 3E+05

7.3304 2-Cyclopenten-1-one, 3-methyl- 3E+05

23.032 Acetophenone, 4'-hydroxy- 2E+05

9.3053 4-Methyl-2H-pyran 2E+05

23.404 Phenol, 2-methoxy-4-propyl- 2E+05

19.638 Ethanone, 1-(2-hydroxy-5-methylphenyl)- 2E+05

20.387 Piperonal 2E+05

24.592 benzoic acid, 4-hydroxy-3-propyl- 2E+05

25.562 Dimethyl-(isopropyl)-silyloxybenzene 1E+05

8.7842 Oxalic acid, pentyl propyl ester 1E+05

58

23.969 6-Methoxy-3-methylbenzofuran 1E+05

17.258 m-Guaiacol 1E+05

28.346 7-Methoxy-1-naphthol 1E+05

8.1352 2,5-Hexanedione 1E+05

14.893 Benzene, 1,2-dimethoxy- 1E+05

13.479 2,4-Dihydroxybenzaldehyde, 2TMS derivative 1E+05

7.7151 1,4-Dimethyl-5-oxabicyclo[2.1.0]pentane 1E+05

24.306 Propane, 2-iodo- 1E+05

31.56 7-Isoquinolinol, 1,2,3,4-tetrahydro-6-methoxy-1-salicyl-

1E+05

22.693 5-Fluoro-2-hydroxyacetophenone 1E+05

12.034 p-Cresol 1E+05

11.491 Furan, 2,3,5-trimethyl- 1E+05

15.782 Benzene, 1,4-dimethoxy- 1E+05

13.209 Isomaltol 9E+04

29.656 3-Phenyl-4-hydroxyacetophenone 5E+04

8.3536 1-Pentanone, 1-(2-furanyl)- 4E+04

28.665 3-Phenyl-4-hydroxyacetophenone 4E+04

29.543 Benzo[d,E]isocoumarin, 3,3-dimethyl- 2E+04

Table 26 - Sample 2L2 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.056 Phenol, 2-methoxy- 6E+08

21.937 Benzaldehyde, 2,4-dihydroxy-6-methyl- 4E+08

24.115 Apocynin 2E+08

25.132 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 1E+08

20.614 Phenol, 2,6-dimethoxy- 6E+07

16.165 Creosol 4E+07

9.6861 Phenol 4E+07

29.853 5'-Hydroxy-2',3',4'-trimethylacetophenone 3E+07

18.608 Phenol, 4-ethyl-2-methoxy- 2E+07

6.5358 Octyl crotonate 1E+07

7.6326 Cyclopentane, 1,2,3,4,5-pentamethyl- 9E+06

8.5541 Octane, 3-methyl-6-methylene- 6E+06

6.2622 Methane-d, trichloro- 6E+06

9.8063 Cyclotetrasiloxane, octamethyl- 6E+06

26.47 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 5E+06

30.887 Anthracene-D10- 5E+06

7.3194 2-Cyclopenten-1-one, 2-methyl- 4E+06

29.788 Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)- 4E+06

28.19 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 4E+06

9.2681 2-Cyclopenten-1-one, 3-methyl- 4E+06

20.993 Benzaldehyde, 4-hydroxy- 3E+06

19.636 2-Methoxy-4-vinylphenol 3E+06

10.389 1,3-Benzodioxole 3E+06

23.252 2-Butanone, 4-(4-hydroxyphenyl)- 3E+06

7.7065 2-Pentanone, 4-hydroxy-4-methyl- 3E+06

9.7333 Azetidine, 3-methyl-3-phenyl- 3E+06

14.883 Benzene, 1,2-dimethoxy- 2E+06

59

25.558 3,4-Dimethoxyphenylacetone 2E+06

21.93 2-Propanone, 1,3-difluoro- 2E+06

20.383 Piperonal 2E+06

11.262 D-Limonene 2E+06

8.7788 Octane, 3-methyl-6-methylene- 2E+06

11.474 2-Cyclopenten-1-one, 2,3-dimethyl- 2E+06

21.026 Phenol, 2-methoxy-4-propyl- 2E+06

23.974 6-Methoxy-3-methylbenzofuran 2E+06

15.779 2-Methoxy-5-methylphenol 2E+06

26.261 4-(1-Hydroxyallyl)-2-methoxyphenol 1E+06

17.271 m-Guaiacol 1E+06

12.716 p-Cresol 1E+06

8.107 2,5-Hexanedione 1E+06

12.46 Acetophenone 1E+06

8.8898 2(3H)-Furanone, dihydro-5-methyl- 1E+06

27.372 2,5-Dihydroxy-4-isopropyl-2,4,6-cycloheptatrien-1-one 1E+06

24.295 Propane, 2-iodo- 1E+06

31.562 4'-Methoxybutyrophenone 1E+06

24.129 2-Naphthyl methyl ketone 1E+06

6.4726 Hexan-2,4-dione, enol 1E+06

8.6 2-Butyl-3,4,5,6-tetrahydropyridine 1E+06

23.043 Acetophenone, 4'-hydroxy- 1E+06

7.5804 Azetidine, 1-nitroso- 1E+06

12.033 Phenol, 2-methyl- 1E+06

24.422 2,6-Dihydroxy-7-methylpurine 1E+06

7.9992 Pyrrolidine 1E+06

30.541 Desaspidinol 1E+06

23.401 Phenol, 2-methoxy-4-propyl- 1E+06

10.116 trans,trans-3,5-Heptadien-2-one 9E+05

8.0522 2-Hexene, 4,4,5-trimethyl- 9E+05

7.4816 Ethanone, 1-(2-furanyl)- 9E+05

7.8269 Ethane, 1,1,2,2-tetrachloro- 9E+05

28.34 7-Methoxy-1-naphthol 8E+05

14.578 Cyclopentasiloxane, decamethyl- 8E+05

10.367 Dihydro-2(3H)-thiophenone 8E+05

17.287 Benzothiazole 8E+05

29.65 2,6-Diisopropylnaphthalene 8E+05

24.101 Benzo[b]thiophene, 2-ethyl- 8E+05

13.679 4-Octene, (E)- 8E+05

13.2 Ethanone, 1-(2-thienyl)- 7E+05

9.1618 Benzaldehyde 7E+05

7.1601 Hexane, 3-ethyl-2-methyl- 7E+05

29.761 1-Acetyl-4,6,8-trimethylazulene 7E+05

20.816 2-Butenoic acid, 2-methyl-, 2-methyl-2-propenyl ester, (E)- 6E+05

14.605 2-Hepten-4-one, 2-methyl- 6E+05

8.3254 2-Cyclopenten-1-one, 3,4-dimethyl- 6E+05

29.532 2,6-Diisopropylnaphthalene 6E+05

16.045 2-Methoxy-5-methylphenol 5E+05

28.653 2,6-Diisopropylnaphthalene 5E+05

60

22.968 3',4'-(Methylenedioxy)acetophenone 5E+05

11.108 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- 5E+05

11.041 Ethanone, 1-(2-furanyl)- 5E+05

22.541 Ethanone, 1-(2-hydroxy-6-methoxyphenyl)- 4E+05

10.188 2-Thiophenecarboxylic acid, 4-nitrophenyl ester 4E+05

28.477 2,6-Diisopropylnaphthalene 4E+05

25.43 Phenol, 2,4-bis(1-methylethyl)-, acetate 4E+05

22.803 5-Fluoro-2-hydroxyacetophenone 4E+05

27.92 2-Butanone, 4-(4-hydroxy-3-methoxyphenyl)- 4E+05

27.792 6-Methoxychroman-2-one 4E+05

12.222 Ethanone, 1-(2-methyl-1-cyclopenten-1-yl)- 4E+05

8.3731 2H-Pyran, 3,4-dihydro-6-methyl- 4E+05

53.771 Dodecane, 1-iodo- 4E+05

12.923 1,2,4-Triazin-3-amine, 5,6-dimethyl- 3E+05

52.522 Tetradecane, 1-iodo- 3E+05

22.124 p-Isopropylphenetole 3E+05

19.527 l-Proline, n-propargyloxycarbonyl-, propargyl ester 3E+05

23.086 3,5-Dimethoxy-4-hydroxytoluene 3E+05

18.269 Benzofuran, 7-methoxy- 3E+05

51.229 Hexadecane, 2-methyl- 3E+05

19.661 Phthalic anhydride 3E+05

19.829 Furan, 2,3,5-trimethyl- 3E+05

13.498 Succinic acid, 2-methylpent-3-yl pentafluorophenyl ester 3E+05

8.205 2H-Pyran-2-one 3E+05

20.763 Phenol, 2-methoxy-4-(1-propenyl)-, acetate 3E+05

19.364 Cyclohexasiloxane, dodecamethyl- 3E+05

30.33 2-(1,1-Dimethylethyl)-6-(1-methylethyl)phenol 2E+05

6.9177 Cyclopropanebutanoic acid, 2,4-dioxo-, methyl ester 2E+05

14.425 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone 2E+05

11.981 2-Butenal, (1-methylethyl)hydrazone 2E+05

47.615 1,4-Benzenedicarboxylic acid, bis(2-ethylhexyl) ester 2E+05

16.511 Heptane, 2,6-dimethyl- 2E+05

19.44 Bicyclo[4.2.1]nonan-9-one 2E+05

49.894 Tetradecane, 1-iodo- 2E+05

15.637 Ethane, 1,1-dimethoxy- 2E+05

36.382 Cyclic octaatomic sulfur 2E+05

27.008 2-(2,4,5-Trimethoxyphenyl)ethylamine, PFP 1E+05

30.417 7-Methoxy-4-methylcoumarin 1E+05

34.206 DL-Alanine, N-methyl-N-(byt-3-yn-1-yloxycarbonyl)-, pentadecyl ester

1E+05

25.006 2,5-Dihydroxy-4-methoxyacetophenone 1E+05

18.796 2H-Inden-2-one, 1,3-dihydro- 1E+05

48.517 2,4,7-Octanetrione 7E+04

31.159 2-Propanol, 1-chloro-, phosphate (3:1) 6E+04

37.479 1H-isoindole-1,3(2H)-dione, 2-(5-methoxy-8-nitro-1-naphthalenyl)-

4E+04

61

Table 27 - Sample 2L3 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.029 Phenol, 2-methoxy- 5E+07

21.922 Vanillin 1E+07

24.119 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 3E+06

6.1842 Methylene chloride 2E+06

25.141 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 1E+06

9.6713 Phenol 6E+05

20.628 Phenol, 2,6-dimethoxy- 6E+05

16.171 2-Methoxy-5-methylphenol 5E+05

29.766 2,6-Diisopropylnaphthalene 3E+05

29.663 2,6-Diisopropylnaphthalene 4E+05

18.608 Phenol, 4-ethyl-2-methoxy- 1E+05

10.377 Glutaric acid, 2-fluorophenyl 4-methoxybenzyl ester 1E+05

28.664 2,6-Diisopropylnaphthalene 3E+05

29.542 2,6-Diisopropylnaphthalene 2E+05

30.904 Phenanthrene-D10 1E+05

29.867 Ethanone, 1-(2,3-dihydro-1,4-benzodioxin-6-yl)- 1E+05

8.7418 5-Chloro-1,3-dimethyl-1H-pyrazole-4-sulfonic acid, 2-methyl-5-trifluoromethyl-2H-pyrazol-3-yl ester

6E+04

28.486 2,6-Diisopropylnaphthalene 1E+05

27.944 Homovanillic acid 7E+04

8.5011 2,4,4-Trimethyl-1-hexene 1E+05

19.639 4-Acetoxy-3-methoxystyrene 5E+04

14.898 Benzene, 1,2-dimethoxy- 8E+04

14.589 Cyclopentasiloxane, decamethyl- 6E+04

28.784 Benzo[d,E]isocoumarin, 3,3-dimethyl- 2E+04

Table 28 - Sample 3L0 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.053 Phenol, 2-methoxy- 6E+08

21.948 4-Hydroxy-2-methoxybenaldehyde 5E+08

25.132 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 1E+08

24.117 Apocynin 2E+08

20.614 Phenol, 2,6-dimethoxy- 5E+07

29.854 6-Methoxychromanone 5E+07

9.6892 Phenol 3E+07

16.167 Creosol 4E+07

30.886 Anthracene-D10- 2E+07

6.5989 N,N-Dimethylacetamide 2E+07

18.605 Phenol, 4-ethyl-2-methoxy- 2E+07

9.809 Cyclotetrasiloxane, octamethyl- 6E+06

26.471 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 6E+06

28.189 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 9E+06

29.788 Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)- 6E+06

8.556 Octane, 3-methyl-6-methylene- 6E+06

23.398 Phenol, 2-methoxy-4-propyl- 4E+06

62

7.6338 Cyclopentane, 1,2,3,4,5-pentamethyl- 8E+06

24.585 1,2-Dimethoxy-4-n-propylbenzene 3E+06

7.3261 2-Cyclopenten-1-one, 2-methyl- 3E+06

20.995 Benzaldehyde, 4-hydroxy- 3E+06

20.383 Piperonal 3E+06

6.2609 2,3-Butanedione 2E+06

10.391 1,3-Benzodioxole 2E+06

21.025 Phenol, 2-methoxy-4-propyl- 1E+06

19.637 2-Methoxy-4-vinylphenol 3E+06

8.6001 3-Butene-1,2-diol, 1-(2-furanyl)- 1E+06

9.2873 2-Cyclopenten-1-one, 3-methyl- 2E+06

8.1103 2,5-Hexanedione 2E+06

26.26 4-(1-Hydroxyallyl)-2-methoxyphenol 2E+06

30.538 Syringylacetone 1E+06

31.557 6-Methoxychromanone 3E+06

7.7042 2-Pentanone, 5-hydroxy- 3E+06

9.7358 Azetidine, 3-methyl-3-phenyl- 3E+06

7.7177 Semustine 1E+06

25.559 Dimethyl-(isopropyl)-silyloxybenzene 1E+06

23.25 2-Butanone, 4-(4-hydroxyphenyl)- 2E+06

7.4849 Ethanone, 1-(2-furanyl)- 9E+05

24.421 Benzaldehyde, 2,4-dihydroxy-3,6-dimethyl- 1E+06

8.9026 2(3H)-Furanone, dihydro-5-methyl- 1E+06

6.4765 Hexan-2,4-dione, enol 9E+05

11.09 1,2-Cyclopentanedione, 3-methyl- 2E+06

23.04 Acetophenone, 4'-hydroxy- 9E+05

7.8272 Ethane, 1,1,2,2-tetrachloro- 1E+06

8.7808 Octane, 3-methyl-6-methylene- 2E+06

12.715 p-Cresol 1E+06

12.463 Acetophenone 1E+06

24.3 Propane, 2-iodo- 1E+06

11.483 2-Cyclopenten-1-one, 2,3-dimethyl- 1E+06

23.974 6-Methoxy-3-methylbenzofuran 2E+06

28.339 7-Methoxy-1-naphthol 1E+06

17.262 m-Guaiacol 1E+06

15.781 2-Methoxy-5-methylphenol 1E+06

7.9981 Oxalic acid, pentyl propyl ester 1E+06

6.5297 2-Pentene, 3-ethyl-2-methyl- 8E+05

27.358 3-Ethoxypyrazolo[3,4-d]pyrimidin-4(5H)-one 1E+06

14.888 Benzene, 1,2-dimethoxy- 1E+06

53.772 Octacosane, 1-iodo- 1E+06

26.07 Ethanone, 1-(3,4-dimethoxyphenyl)- 6E+05

13.346 2-Pyrrolidinecarboxylic acid, 1,2-dimethyl-5-oxo-, methyl ester

5E+05

52.518 Hexacosane, 1-iodo- 1E+06

7.1629 Acetaldehyde, ethylidenehydrazone 6E+05

51.228 Tetracosane, 1-iodo- 1E+06

14.577 Cyclopentasiloxane, decamethyl- 9E+05

18.175 3,4-Dimethyl-5-hydroxy-isoxazole 7E+05

63

12.035 p-Cresol 8E+05

11.263 Bicyclo[3.1.0]hex-2-ene, 4-methyl-1-(1-methylethyl)- 1E+06

22.969 3',4'-(Methylenedioxy)acetophenone 5E+05

24.134 Propane, 2-iodo- 6E+05

29.65 2,6-Diisopropylnaphthalene 6E+05

8.0529 2-Heptene, 5-ethyl-2,4-dimethyl- 1E+06

24.099 Benzo[b]thiophene, 2-ethyl- 8E+05

16.046 2-Methoxy-5-methylphenol 6E+05

13.203 Isomaltol 3E+05

19.529 2-Hydroxy-3-methoxybenzaldehyde, acetate 5E+05

12.923 1,2,4-Triazin-3-amine, 5,6-dimethyl- 4E+05

55.052 Tetracosane, 1-iodo- 6E+05

23.086 3-Hydroxy-4-methoxybenzoic acid 4E+05

49.895 Tetracosane, 1-iodo- 6E+05

13.672 1,4-Cyclohexanedione 6E+05

29.532 2,6-Diisopropylnaphthalene 5E+05

28.654 2,6-Diisopropylnaphthalene 4E+05

25.425 Ethanone, 1-(2,3-dihydro-1,4-benzodioxin-6-yl)- 4E+05

24.895 3-Hydroxy-4-methoxybenzoic acid, methyl ester 3E+05

9.1656 S-Phenyl benzothioate 6E+05

11.981 2-Cyclopenten-1-one, 2-hydroxy-3,4-dimethyl- 4E+05

28.48 2,6-Diisopropylnaphthalene 4E+05

25.006 2,5-Dihydroxy-4-methoxyacetophenone 2E+05

20.767 Phenol, 2-methoxy-4-(1-propenyl)-, acetate 3E+05

8.3303 2-Cyclopenten-1-one, 3,4-dimethyl- 3E+05

29.762 Benzenesulfonamide, 4-methyl-N-ethyl-N-undecyl- 7E+05

22.547 Ethanone, 1-(2-hydroxy-6-methoxyphenyl)- 3E+05

29.611 5'-Hydroxy-2',3',4'-trimethylacetophenone 2E+05

6.9197 Cyclopropanebutanoic acid, 2,4-dioxo-, methyl ester 2E+05

48.515 Dodecane, 1-iodo- 3E+05

18.271 1H-Benzimidazole, 5-methoxy- 2E+05

10.97 Benzene, 1,2,3-trimethyl- 3E+05

36.386 Cyclic octaatomic sulfur 2E+05

30.32 N-Methylcoclaurine 2E+05

14.458 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone 3E+05

47.624 Terephthalic acid, di(4-octyl) ester 2E+05

18.683 4-Formyl-3,5-dimethyl-1H-pyrrole-2-carbonitrile 3E+05

34.322 L-Alanine, 2-methyl-N-(n-butyl)-N-(4-methylphenyl)-, n-butyl ester

2E+05

27.793 D-Alanine, N-(4-anisoyl)-, undecyl ester 2E+05

42.254 Octadecanoic acid, butyl ester 2E+05

19.365 Cyclohexasiloxane, dodecamethyl- 2E+05

11.788 Benzene, (methoxymethyl)- 2E+05

12.227 Phenol, 2-methoxy- 2E+05

38.841 Hexadecanoic acid, butyl ester 1E+05

18.796 1H-Inden-1-one, 2,3-dihydro- 1E+05

30.417 7-Methoxy-4-methylcoumarin 7E+04

37.474 1H-isoindole-1,3(2H)-dione, 2-(5-methoxy-8-nitro-1-naphthalenyl)-

6E+04

64

Table 29 - Sample 3L1 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.054 Phenol, 2-methoxy- 6E+08

21.938 Vanillin 5E+08

24.115 Apocynin 2E+08

25.131 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 1E+08

20.613 Phenol, 2,6-dimethoxy- 6E+07

16.166 Creosol 4E+07

29.852 6-Methoxychromanone 4E+07

9.6868 Phenol 3E+07

18.605 Phenol, 4-ethyl-2-methoxy- 2E+07

6.2736 Methylene chloride 2E+07

6.6441 N,N-Dimethylacetamide 1E+07

9.8122 Cyclotetrasiloxane, octamethyl- 9E+06

7.632 Cyclopentane, 1,2,3,4,5-pentamethyl- 8E+06

28.186 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 7E+06

38.839 Hexadecanoic acid, butyl ester 7E+06

30.886 Anthracene-D10- 6E+06

8.5544 Octane, 3-methyl-6-methylene- 6E+06

26.47 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 6E+06

29.787 Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)- 5E+06

20.991 Benzaldehyde, 4-hydroxy- 4E+06

7.3253 2-Cyclopenten-1-one, 2-methyl- 4E+06

42.255 Octadecanoic acid, butyl ester 4E+06

17.281 1,2-Benzisothiazole 3E+06

11.27 D-Limonene 3E+06

39.239 Acetic acid n-octadecyl ester 3E+06

36.379 Cyclic octaatomic sulfur 3E+06

19.636 2-Methoxy-4-vinylphenol 3E+06

9.2821 2-Cyclopenten-1-one, 3-methyl- 3E+06

9.7346 Azetidine, 3-methyl-3-phenyl- 2E+06

7.7049 2-Ethyl-3-vinyloxirane 2E+06

20.382 Piperonal 2E+06

25.556 3,4-Dimethoxyphenylacetone 2E+06

31.554 6-Methoxychromanone 2E+06

10.39 1,3-Benzodioxole 2E+06

26.257 4-(1-Hydroxyallyl)-2-methoxyphenol 2E+06

27.946 Benzenepropanol, 4-hydroxy-3-methoxy- 2E+06

8.76 3-Hydroxy-4-methoxybenzaldehyde, TBDMS 2E+06

23.971 6-Methoxy-3-methylbenzofuran 2E+06

21.024 Phenol, 2-methoxy-4-propyl- 2E+06

11.478 Norbornadieone 2E+06

8.78 Octane, 3-methyl-6-methylene- 2E+06

24.296 2,5-Dimethoxythiophenol 1E+06

15.781 Creosol 1E+06

17.264 m-Guaiacol 1E+06

12.714 p-Cresol 1E+06

65

24.585 benzoic acid, 4-hydroxy-3-propyl- 1E+06

12.46 Acetophenone 1E+06

23.249 Phenol, 2-methoxy-4-(1-propenyl)- 1E+06

30.54 Syringylacetone 1E+06

8.1151 2,5-Hexanedione 1E+06

23.399 Phenol, 2-methoxy-4-propyl- 1E+06

42.482 Tetracosane, 1-iodo- 1E+06

23.036 Acetophenone, 4'-hydroxy- 1E+06

13.485 2,5-Dihydroxybenzaldehyde, 2TMS derivative 1E+06

28.339 7-Methoxy-1-naphthol 1E+06

14.885 Benzene, 1,2-dimethoxy- 1E+06

14.578 Cyclopentasiloxane, decamethyl- 1E+06

8.5973 2-Butyl-3,4,5,6-tetrahydropyridine 1E+06

8.899 2(3H)-Furanone, dihydro-5-methyl- 1E+06

27.355 Quinoline, decahydro-2,5-dipropyl- 1E+06

45.608 Hexacosane, 1-iodo- 1E+06

8.0545 2-Heptene, 5-ethyl-2,4-dimethyl- 1E+06

7.8242 Ethane, 1,1,2,2-tetrachloro- 9E+05

12.032 Phenol, 2-methyl- 9E+05

24.132 2,4,6,(1H,3H,5H)-Pyrimidinetrione, 5-acetyl- 9E+05

7.4835 Ethanone, 1-(2-furanyl)- 9E+05

6.5294 3-Hexene, 2,3-dimethyl- 9E+05

29.649 2,6-Diisopropylnaphthalene 9E+05

10.38 Dihydro-2(3H)-thiophenone 8E+05

10.119 trans,trans-3,5-Heptadien-2-one 8E+05

24.096 Benzo[b]thiophene, 2-ethyl- 8E+05

6.4769 Hexan-2,4-dione, enol 8E+05

48.512 Tetracosane, 1-iodo- 8E+05

24.42 Benzaldehyde, 2,4-dihydroxy-3,6-dimethyl- 8E+05

11.097 1,2-Cyclopentanedione, 3-methyl- 8E+05

7.9936 Pyrrolidine 7E+05

29.759 3-Phenyl-4-hydroxyacetophenone 7E+05

7.1636 Hexane, 3-ethyl-2-methyl- 7E+05

9.6007 (S)-(+)-Isoleucinol 6E+05

16.044 2-Methoxy-5-methylphenol 6E+05

19.826 2-Cyclopenten-1-one, 3,4-dimethyl- 6E+05

51.228 Hexadecane, 1-iodo- 6E+05

22.717 Phenol, 2,6-dimethoxy-, acetate 6E+05

44.075 Dodecane, 1-iodo- 6E+05

14.609 3-Oxobutan-2-yl (E)-2-methylbut-2-enoate 6E+05

49.892 Hexadecane, 1-iodo- 6E+05

39.096 Decane, 1-iodo- 6E+05

42.618 1,7-Dimethyl-4-(1-methylethyl)cyclodecane 6E+05

27.013 2-(Methylmercapto)benzothiazole 5E+05

28.653 3-Phenyl-4-hydroxyacetophenone 5E+05

29.534 2,6-Diisopropylnaphthalene 5E+05

28.476 2,6-Diisopropylnaphthalene 5E+05

47.084 Decane, 1-iodo- 5E+05

22.965 3',4'-(Methylenedioxy)acetophenone 5E+05

66

53.771 Hexacosane, 1-iodo- 5E+05

52.519 Tetradecane, 1-iodo- 5E+05

9.1649 Phenylglyoxylic Acid, 3-methylbutyl ester 5E+05

23.086 3,5-Dimethoxy-4-hydroxytoluene 5E+05

13.655 7-Oxabicyclo[4.1.0]heptan-2-one 5E+05

11.046 Ethanone, 1-(2-furanyl)- 4E+05

13.201 Ethanone, 1-(2-thienyl)- 4E+05

47.618 1,4-Benzenedicarboxylic acid, bis(2-ethylhexyl) ester 4E+05

36.573 Disulfide, bis(4-methylphenyl) 4E+05

11.981 2-Cyclopenten-1-one, 2-hydroxy-3,4-dimethyl- 4E+05

8.3264 2-Cyclopenten-1-one, 3,4-dimethyl- 4E+05

30.326 2-methyl-3-((trimethylsilyl)ethynyl)cyclopent-2-en-1-one 3E+05

15.499 Benzeneethanol, 4-hydroxy- 3E+05

22.544 Ethanone, 1-(2-hydroxy-6-methoxyphenyl)- 3E+05

19.364 Cyclohexasiloxane, dodecamethyl- 3E+05

12.923 1,2,4-Triazin-3-amine, 5,6-dimethyl- 3E+05

25.424 Ethanone, 1-(2,3-dihydro-1,4-benzodioxin-6-yl)- 3E+05

20.765 Phenol, 2-methoxy-4-(1-propenyl)-, acetate 3E+05

14.424 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone 3E+05

8.3717 1,2,4,5-Tetrazin-3-amine 3E+05

13.359 2-Pyrrolidinecarboxylic acid, 1,2-dimethyl-5-oxo-, methyl ester 3E+05

6.916 5-Ethyl-2-octen-4-one 3E+05

12.223 2-Cyclopenten-1-one, 3,4,4-trimethyl- 3E+05

18.271 Benzofuran, 7-methoxy- 3E+05

52.186 .beta.-Sitosterol, propionate 3E+05

24.805 Hexathiane 3E+05

26.068 4',6'-Dihydroxy-2',3'-dimethylacetophenone 3E+05

17.037 Phenol, 2-methoxy- 2E+05

22.118 2,4,6-Cycloheptatrien-1-one, 2-hydroxy-5-(1-methylethyl)- 2E+05

10.189 2-Thiophenecarboxaldehyde 2E+05

25.355 5-Amino-2-methyl-2H-tetrazole 2E+05

14.683 1,2,4-Trithiolane, 3,5-dimethyl- 2E+05

16.51 3,4-Hexanedione, 2,2,5-trimethyl- 2E+05

17.891 Benzaldehyde, 2,4-dihydroxy-6-methyl- 2E+05

27.791 2,4(1H,3H)-Pteridinedione, 8-methyl- 2E+05

18.696 3,6-Dimethylpiperazine-2,5-dione 2E+05

22.03 3,4-Hexanedione, 2,2,5-trimethyl- 2E+05

25.005 2,5-Dihydroxy-4-methoxyacetophenone 2E+05

40.821 Nonane, 5-methyl-5-propyl- 2E+05

14.007 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone 2E+05

19.443 Bicyclo[4.2.1]nonan-9-one 2E+05

34.317 L-Alanine, 2-methyl-N-(n-butyl)-N-(4-methylphenyl)-, n-butyl ester 1E+05

37.478 1H-isoindole-1,3(2H)-dione, 2-(5-methoxy-8-nitro-1-naphthalenyl)- 8E+04

21.501 Silane, diethyloctadecyloxy(2-methoxyethoxy)- 6E+04

31.156 2-Propanol, 1-chloro-, phosphate (3:1) 6E+04

67

Table 30 - Sample 3L2 ordered from highest component area to lowest

Component RT Compound Name Component Area

21.951 Vanillin 6E+08

13.056 2-n-Butyl furan 5E+08

24.122 Apocynin 3E+08

25.137 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 2E+08

20.613 Phenol, 2,6-dimethoxy- 1E+08

13.074 Pyridine, 4-methoxy-1-oxide- 1E+08

16.164 Creosol 8E+07

29.856 5'-Hydroxy-2',3',4'-trimethylacetophenone 7E+07

27.954 Benzenepropanol, 4-hydroxy-3-methoxy- 6E+07

9.684 Phenol 6E+07

18.601 Phenol, 4-ethyl-2-methoxy- 4E+07

6.2706 Methylene chloride 1E+07

26.469 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 1E+07

28.187 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 1E+07

29.788 Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)- 1E+07

7.6348 Cyclopentane, 1,2,3,4,5-pentamethyl- 9E+06

30.886 Anthracene-D10- 9E+06

6.6305 N,N-Dimethylacetamide 9E+06

36.381 Cyclic octaatomic sulfur 9E+06

20.992 Benzaldehyde, 4-hydroxy- 8E+06

23.246 2-Butanone, 4-(4-hydroxyphenyl)- 8E+06

38.84 Hexadecanoic acid, butyl ester 8E+06

9.8093 Cyclotetrasiloxane, octamethyl- 7E+06

42.258 Octadecanoic acid, butyl ester 7E+06

7.3189 2-Cyclopenten-1-one, 2-methyl- 7E+06

8.5556 Octane, 3-methyl-6-methylene- 7E+06

9.2489 2,4-Dimethylfuran 6E+06

25.556 3,4-Dimethoxyphenylacetone 5E+06

39.241 1-Octadecanol 5E+06

17.276 1,2-Benzisothiazole 5E+06

21.023 Phenol, 2-methoxy-4-propyl- 5E+06

19.633 2-Methoxy-4-vinylphenol 4E+06

31.554 4'-Methoxybutyrophenone 4E+06

26.255 4-(1-Hydroxyallyl)-2-methoxyphenol 4E+06

24.296 3,4-Dimethoxythiophenol 4E+06

15.775 Phenol, 2-methoxy-3-methyl- 4E+06

30.541 Syringylacetone 3E+06

23.972 6-Methoxy-3-methylbenzofuran 3E+06

23.033 1-Butanone, 4-chloro-1-(4-hydroxyphenyl)- 3E+06

12.722 p-Cresol 3E+06

11.471 Norbornadieone 3E+06

9.7345 Azetidine, 3-methyl-3-phenyl- 3E+06

10.39 1,3-Benzodioxole 3E+06

7.5708 Butyrolactone 3E+06

7.7061 3-Ethyl-4-methylpentan-1-ol 3E+06

68

12.457 Acetophenone 3E+06

20.38 Piperonal 3E+06

17.251 m-Guaiacol 2E+06

28.339 7-Methoxy-1-naphthol 2E+06

8.8799 2(3H)-Furanone, dihydro-5-methyl- 2E+06

12.029 Phenol, 2-methyl- 2E+06

42.485 Octadecane, 2-methyl- 2E+06

48.518 Tetracosane, 1-iodo- 2E+06

45.614 Docosane, 1-iodo- 2E+06

51.228 Tetracosane, 1-iodo- 2E+06

49.893 Tetracosane, 1-iodo- 2E+06

8.7801 Octane, 3-methyl-6-methylene- 2E+06

7.4773 Ethanone, 1-(2-furanyl)- 2E+06

10.11 Furan, 2-ethyl-5-methyl- 2E+06

14.882 Benzene, 1,2-dimethoxy- 2E+06

8.105 2,5-Hexanedione 2E+06

23.399 Phenol, 2-methoxy-4-propyl- 2E+06

24.135 Propane, 1-iodo- 2E+06

24.418 Benzaldehyde, 2,4-dihydroxy-3,6-dimethyl- 2E+06

27.357 3-Ethoxypyrazolo[3,4-d]pyrimidin-4(5H)-one 2E+06

52.519 Hexacosane, 1-iodo- 2E+06

27.383 2-Butanone, 4-(4-hydroxy-3-methoxyphenyl)- 1E+06

8.0564 2,3,3-Trimethyl-1-hexene 1E+06

31.578 3-Buten-2-one, 4-(4-hydroxy-3-methoxyphenyl)- 1E+06

22.744 5-Fluoro-2-hydroxyacetophenone 1E+06

53.774 Tetracosane, 1-iodo- 1E+06

47.089 Tetracosane, 1-iodo- 1E+06

28.195 Ethanone, 1-[5-(2-furanylmethyl)-2-furanyl]- 1E+06

8.5984 3-Butene-1,2-diol, 1-(2-furanyl)- 1E+06

44.076 Hexadecane, 1-iodo- 1E+06

13.206 Ethanone, 1-(2-thienyl)- 1E+06

16.041 2-Methoxy-5-methylphenol 1E+06

10.365 Dihydro-2(3H)-thiophenone 1E+06

24.584 benzoic acid, 4-hydroxy-3-propyl- 1E+06

14.926 1,2,4-Trithiolane, 3,5-dimethyl- 1E+06

8.7762 3-Hydroxy-4-methoxybenzaldehyde, TBDMS 1E+06

14.603 3-Oxobutan-2-yl (E)-2-methylbut-2-enoate 1E+06

34.149 5,10-Diethoxy-2,3,7,8-tetrahydro-1H,6H-dipyrrolo[1,2-a:1',2'-d]pyrazine 1E+06

23.086 3,5-Dimethoxy-4-hydroxytoluene 1E+06

8.0008 Methacrolein 1E+06

42.62 Oxalic acid, allyl octadecyl ester 1E+06

24.803 Hexathiane 1E+06

11.265 Cyclobutane, 1,2-dipropenyl- 1E+06

23.341 Vanillin 1E+06

6.5323 3-Hexene, 2,3-dimethyl- 1E+06

29.652 2,6-Diisopropylnaphthalene 1E+06

12.113 1-Azabicyclo[3.1.0]hexane 9E+05

14.685 1,2,4-Trithiolane, 3,5-dimethyl- 9E+05

9.5976 (S)-(+)-Isoleucinol 9E+05

69

7.828 Ethane, 1,1,2,2-tetrachloro- 9E+05

39.096 Undecane, 3,8-dimethyl- 9E+05

11.038 1-(3H-Imidazol-4-yl)-ethanone 9E+05

24.093 Benzo[b]thiophene, 2-ethyl- 8E+05

6.4798 Hexan-2,4-dione, enol 8E+05

27.791 6-Methoxychroman-2-one 8E+05

11.098 1,2-Cyclopentanedione, 3-methyl- 8E+05

7.1623 2,3,4,5-Tetrahydropyridazine 8E+05

15.268 Pentanoic acid, 5-nitro-, methyl ester 8E+05

14.574 Cyclopentasiloxane, decamethyl- 8E+05

10.189 2-Thiophenecarboxylic acid, 4-nitrophenyl ester 8E+05

19.524 Oxypurinol 7E+05

19.827 Carvenone 7E+05

17.787 1H-Imidazole-4-carboxaldehyde 7E+05

9.1605 Ethanone, 2-(formyloxy)-1-phenyl- 7E+05

28.655 2,6-Diisopropylnaphthalene 7E+05

25.66 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 7E+05

8.3278 2-Cyclopenten-1-one, 3,4-dimethyl- 7E+05

27.921 1-Methyl-2,5-dipropyldecahydroquinoline 7E+05

22.543 Ethanone, 1-(2-hydroxy-6-methoxyphenyl)- 7E+05

55.054 Tetracosane, 1-iodo- 7E+05

20.766 Phenol, 2-methoxy-4-(2-propenyl)-, acetate 7E+05

31.793 Hydantoin, 1-butyl- 6E+05

28.478 2,6-Diisopropylnaphthalene 6E+05

22.965 3',4'-(Methylenedioxy)acetophenone 6E+05

29.534 2,6-Diisopropylnaphthalene 6E+05

47.627 1,4-Benzenedicarboxylic acid, bis(2-ethylhexyl) ester 6E+05

25.427 5'-Hydroxy-2',3',4'-trimethylacetophenone 6E+05

13.645 4-Hexen-3-one, 5-methyl- 6E+05

18.691 3,6-Dimethylpiperazine-2,5-dione 6E+05

12.941 1,2,4-Triazin-3-amine, 5,6-dimethyl- 6E+05

18.155 Phenol, 4-ethyl-2-methoxy- 5E+05

29.61 5'-Hydroxy-2',3',4'-trimethylacetophenone 5E+05

30.331 1,4-Benzenediamine, N,N'-bis(1-methylethyl)- 5E+05

18.271 Benzofuran, 7-methoxy- 5E+05

15.635 o-n-Propylhydroxylamine 5E+05

52.186 .beta.-Sitosterol, propionate 4E+05

29.761 Benzenesulfonamide, 4-methyl-N-ethyl-N-undecyl- 4E+05

36.572 Disulfide, bis(4-methylphenyl) 4E+05

31.923 2-(1,1-Dimethylethyl)-6-(1-methylethyl)phenol 4E+05

19.917 3-Amino-4,6-dimethylpyridone-2(1H) 4E+05

13.356 2-Pyrrolidinecarboxylic acid, 1,2-dimethyl-5-oxo-, methyl ester 4E+05

18.36 Nonanoic acid 4E+05

32.191 Cyclo(L-prolyl-L-valine) 4E+05

11.779 .beta.-Methoxy-.alpha.-phenylphenethyl alcohol 4E+05

11.985 2-Cyclopenten-1-one, 2-hydroxy-3,4-dimethyl- 4E+05

13.86 4(3H)-Pyrimidinone, 2,3,6-trimethyl- 4E+05

25.007 2,5-Dihydroxy-4-methoxyacetophenone 4E+05

19.437 Bicyclo[4.2.1]nonan-9-one 3E+05

70

40.824 Borane, diethyl(decyloxy)- 3E+05

8.3758 2H-Pyran, 3,4-dihydro-6-methyl- 3E+05

15.303 1,4-Benzenediol, 2-methoxy- 3E+05

33.745 d-Proline, n-butoxycarbonyl-, octyl ester 3E+05

14.423 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone 3E+05

16.68 2-Acetyl-5-methylthiophene 3E+05

8.9208 Dihydro-3-(2H)-thiophenone 2E+05

10.435 2-Methyl-1,3-dithiacyclopentane 2E+05

19.364 Cyclohexasiloxane, dodecamethyl- 2E+05

7.0154 2(3H)-Furanone, 5-methyl- 2E+05

18.793 2H-Inden-2-one, 1,3-dihydro- 2E+05

39.442 [1,1'-Biphenyl]-4,4'-diol, 3,3'-dimethoxy- 2E+05

37.477 1H-isoindole-1,3(2H)-dione, 2-(5-methoxy-8-nitro-1-naphthalenyl)- 2E+05

30.409 7-Methoxy-4-methylcoumarin 2E+05

13.259 2-Furancarboxylic acid, tetrahydro-3-methyl-5-oxo- 2E+05

31.16 2-Propanol, 1-chloro-, phosphate (3:1) 8E+04

52.166 2,6-Difluorobenzoic acid, phenyl ester 7E+04

Table 31 - Sample 3L3 ordered from highest component area to lowest

Component RT Compound Name Component Area

21.948 4-Hydroxy-2-methoxybenaldehyde 6E+08

13.057 Tetrazolo[1,5-b]pyridazine 3E+08

24.122 Apocynin 3E+08

25.136 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 2E+08

20.613 Phenol, 2,6-dimethoxy- 1E+08

27.955 Benzenepropanol, 4-hydroxy-3-methoxy- 1E+08

13.075 Pyridine, 4-methoxy-1-oxide- 9E+07

16.162 Creosol 9E+07

29.856 5'-Hydroxy-2',3',4'-trimethylacetophenone 7E+07

9.6841 Phenol 6E+07

18.6 Phenol, 4-ethyl-2-methoxy- 4E+07

6.2729 Methane-d, trichloro- 1E+07

26.469 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 1E+07

38.84 Hexadecanoic acid, butyl ester 1E+07

29.788 Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)- 1E+07

28.187 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 1E+07

20.989 Benzaldehyde, 4-hydroxy- 1E+07

7.6332 Cyclopentane, 1,2,3,4,5-pentamethyl- 9E+06

7.3176 2-Cyclopenten-1-one, 2-methyl- 7E+06

9.2449 2-Cyclopenten-1-one, 3-methyl- 7E+06

9.8103 Cyclotetrasiloxane, octamethyl- 7E+06

30.886 Anthracene-D10- 7E+06

8.5548 Octane, 3-methyl-6-methylene- 6E+06

25.556 3,4-Dimethoxyphenylacetone 6E+06

42.259 Octadecanoic acid, butyl ester 6E+06

36.38 Cyclic octaatomic sulfur 5E+06

26.256 4-(1-Hydroxyallyl)-2-methoxyphenol 5E+06

21.023 Phenol, 2-methoxy-4-propyl- 5E+06

71

19.632 2-Methoxy-4-vinylphenol 5E+06

15.777 Creosol 4E+06

39.242 1-Hexadecanol, acetate 4E+06

23.247 Phenol, 2-methoxy-6-(2-propenyl)- 4E+06

17.276 1,2-Benzisothiazole 4E+06

31.557 6-Methoxychromanone 4E+06

23.03 Ethanone, 1-(3-hydroxyphenyl)- 4E+06

30.539 Syringylacetone 4E+06

24.296 3,4-Dimethoxythiophenol 4E+06

12.722 p-Cresol 4E+06

23.971 6-Methoxy-3-methylbenzofuran 3E+06

10.389 1,3-Benzodioxole 3E+06

11.47 2-Cyclopenten-1-one, 2,3-dimethyl- 3E+06

7.5687 Butyrolactone 3E+06

9.7337 Azetidine, 3-methyl-3-phenyl- 3E+06

17.25 m-Guaiacol 3E+06

12.456 Acetophenone 2E+06

28.339 7-Methoxy-1-naphthol 2E+06

8.8759 2(3H)-Furanone, dihydro-5-methyl- 2E+06

20.382 Piperonal 2E+06

12.028 Phenol, 2-methyl- 2E+06

27.382 2-Butanone, 4-(4-hydroxy-3-methoxyphenyl)- 2E+06

23.397 Phenol, 2-methoxy-4-propyl- 2E+06

10.108 Furan, 2-ethyl-5-methyl- 2E+06

14.882 Benzene, 1,2-dimethoxy- 2E+06

7.7105 2-Pyrazoline, 1-isobutyl-3-methyl- 2E+06

7.4764 Ethanone, 1-(2-furanyl)- 2E+06

8.7813 Octane, 3-methyl-6-methylene- 2E+06

13.206 Ethanone, 1-(2-thienyl)- 2E+06

42.482 Tetracosane, 1-iodo- 2E+06

8.5983 3-Butene-1,2-diol, 1-(2-furanyl)- 1E+06

16.038 2-Methoxy-5-methylphenol 1E+06

8.1084 2,5-Hexanedione 1E+06

31.578 3-Buten-2-one, 4-(4-hydroxy-3-methoxyphenyl)- 1E+06

22.719 Phenol, 2,6-dimethoxy-, acetate 1E+06

23.085 3,5-Dimethoxy-4-hydroxytoluene 1E+06

24.136 2,4,6,(1H,3H,5H)-Pyrimidinetrione, 5-acetyl- 1E+06

14.603 2-Hepten-4-one, 2-methyl- 1E+06

10.364 Dihydro-2(3H)-thiophenone 1E+06

34.152 5,10-Diethoxy-2,3,7,8-tetrahydro-1H,6H-dipyrrolo[1,2-a:1',2'-d]pyrazine

1E+06

45.607 Docosane, 1-iodo- 1E+06

14.924 1,2,4-Trithiolane, 3,5-dimethyl- 1E+06

7.8255 Ethane, 1,1,2,2-tetrachloro- 1E+06

15.266 Cyclobutanecarboxylic acid, 3,5-difluorophenyl ester 1E+06

29.766 Benzo[d,E]isocoumarin, 3,3-dimethyl- 1E+06

7.9984 Methacrolein 1E+06

11.271 Bicyclo[3.1.0]hex-2-ene, 4-methyl-1-(1-methylethyl)- 1E+06

24.419 Benzaldehyde, 2,4-dihydroxy-3,6-dimethyl- 1E+06

72

48.513 Tetracosane, 1-iodo- 1E+06

23.341 Benzaldehyde, 3-hydroxy-4-methoxy- 1E+06

15.482 Benzeneethanol, 4-hydroxy- 1E+06

29.651 2,6-Diisopropylnaphthalene 1E+06

24.093 Benzene, 1-methyl-4-[(methylthio)ethynyl]- 1E+06

8.0528 2-Heptene, 5-ethyl-2,4-dimethyl- 1E+06

14.684 1,2,4-Trithiolane, 3,5-dimethyl- 9E+05

15.635 o-n-Propylhydroxylamine 9E+05

27.791 6-Methoxychroman-2-one 9E+05

31.794 Hydantoin, 1-butyl- 9E+05

19.522 Benzaldehyde, 2-hydroxy-3-methoxy- 9E+05

18.055 1,2-Benzenediol, 3-methoxy- 9E+05

11.037 1-(3H-Imidazol-4-yl)-ethanone 9E+05

6.5302 3-Hexene, 2,3-dimethyl- 9E+05

14.577 Cyclopentasiloxane, decamethyl- 9E+05

51.225 Triacontane 9E+05

27.922 1-Methyl-2,5-dipropyldecahydroquinoline 9E+05

49.892 Tetracosane, 1-iodo- 8E+05

11.098 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- 8E+05

44.076 Hexadecane, 1-iodo- 8E+05

42.619 Pentyl tetratriacontyl ether 8E+05

8.3283 2-Cyclopenten-1-one, 3,4-dimethyl- 8E+05

17.014 2-Acetyl-5-methylfuran 8E+05

47.085 Hexadecane, 1-iodo- 8E+05

28.657 2,6-Diisopropylnaphthalene 7E+05

19.825 Carvenone 7E+05

28.479 2,6-Diisopropylnaphthalene 7E+05

29.534 2,6-Diisopropylnaphthalene 7E+05

24.586 benzoic acid, 4-hydroxy-3-propyl- 7E+05

12.398 Ethanone, 1-(1H-pyrrol-2-yl)- 7E+05

52.517 Tetracosane, 1-iodo- 7E+05

9.1586 Ethanone, 2-(formyloxy)-1-phenyl- 7E+05

20.763 Phenol, 2-methoxy-4-(1-propenyl)-, (Z)- 7E+05

22.542 2-Hydroxy-3-methoxyacetophenone 7E+05

26.07 Ethanone, 1-(3,4-dimethoxyphenyl)- 7E+05

39.097 Undecane, 3,8-dimethyl- 6E+05

12.064 2-Methylbutanoic anhydride 6E+05

53.771 Tetracosane, 1-iodo- 6E+05

18.154 Phenol, 4-ethyl-2-methoxy- 6E+05

10.417 2-Thiophenecarboxaldehyde 6E+05

22.966 3',4'-(Methylenedioxy)acetophenone 6E+05

22.123 Phenol, 2-methoxy-4-(1-propenyl)-, (Z)- 6E+05

16.293 1,2-Benzenediol, mono(methylcarbamate) 6E+05

30.329 2-(1,1-Dimethylethyl)-6-(1-methylethyl)phenol 6E+05

25.424 Phenol, 2,4-bis(1-methylethyl)-, acetate 6E+05

32.192 Cyclo(L-prolyl-L-valine) 6E+05

34.209 l-Norvaline, n-propargyloxycarbonyl-, isohexyl ester 6E+05

10.182 2-Thiophenecarboxaldehyde 5E+05

12.22 2-Cyclopenten-1-one, 2,3,4-trimethyl- 5E+05

73

17.782 1H-Imidazole-4-carboxaldehyde 5E+05

24.803 Hexathiane 5E+05

49.77 3,4-Divanillyltetrahydrofuran 5E+05

31.923 2-(1,1-Dimethylethyl)-6-(1-methylethyl)phenol 5E+05

18.268 1H-Benzimidazole, 5-methoxy- 5E+05

47.617 1,4-Benzenedicarboxylic acid, bis(2-ethylhexyl) ester 5E+05

13.499 2,4-Dihydroxybenzaldehyde, 2TMS derivative 5E+05

36.577 Disulfide, bis(4-methylphenyl) 5E+05

19.914 3-Amino-4,6-dimethylpyridone-2(1H) 5E+05

25.009 2,5-Dihydroxy-4-methoxyacetophenone 4E+05

19.357 Cyclohexasiloxane, dodecamethyl- 4E+05

19.439 Bicyclo[4.2.1]nonan-9-one 4E+05

35.126 Butyl myristate 4E+05

33.747 d-Proline, n-butoxycarbonyl-, octyl ester 3E+05

15.3 1,4-Benzenediol, 2-methoxy- 3E+05

35.732 Difenoxin 3E+05

14.428 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone 3E+05

39.44 [1,1'-Biphenyl]-4,4'-diol, 3,3'-dimethoxy- 3E+05

18.794 2H-Inden-2-one, 1,3-dihydro- 3E+05

8.3806 Cyclohexane, 1-ethyl-1-methyl- 3E+05

11.987 2-Cyclopenten-1-one, 2-hydroxy-3,4-dimethyl- 3E+05

17.89 Benzaldehyde, 2,4-dihydroxy-6-methyl- 3E+05

40.822 Borane, diethyl(decyloxy)- 3E+05

13.354 Pyrimidine, 1,4,5,6-tetrahydro-1,2-dimethyl- 3E+05

37.48 9H-Xanthen-9-one, 1-hydroxy-3,5,6-trimethoxy- 2E+05

40.322 Silane, diethylnonyloxypropoxy- 2E+05

23.699 3',4'-(Methylenedioxy)acetophenone 2E+05

13.257 5-Amino-2-methyl-2H-tetrazole 2E+05

22.03 3,4-Hexanedione, 2,2,5-trimethyl- 1E+05

33.016 .beta.-Carboline, 8-methoxy-1-methyl- 1E+05

Table 32 - Sample 3L4 ordered from highest component area to lowest

Component RT

Compound Name Component Area

21.948 4-Hydroxy-2-methoxybenaldehyde 6E+08

13.056 2-n-Butyl furan 6E+08

24.121 Apocynin 4E+08

25.137 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 2E+08

27.953 Benzenepropanol, 4-hydroxy-3-methoxy- 2E+08

20.613 Phenol, 2,6-dimethoxy- 1E+08

16.163 Creosol 1E+08

13.082 Pyridine, 4-methoxy-1-oxide- 9E+07

9.6849 Phenol 7E+07

29.855 5'-Hydroxy-2',3',4'-trimethylacetophenone 7E+07

6.292 Methylene chloride 5E+07

18.599 Phenol, 4-ethyl-2-methoxy- 5E+07

36.381 Cyclic octaatomic sulfur 2E+07

28.186 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 2E+07

38.839 Hexadecanoic acid, butyl ester 2E+07

74

26.466 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 2E+07

39.241 Acetic acid n-octadecyl ester 1E+07

29.786 Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)- 1E+07

42.258 Octadecanoic acid, butyl ester 1E+07

23.239 2-Butanone, 4-(4-hydroxyphenyl)- 1E+07

20.989 Benzaldehyde, 4-hydroxy- 1E+07

6.6481 N,N-Dimethylacetamide 1E+07

9.2398 2-Cyclopenten-1-one, 3-methyl- 9E+06

45.612 Heptacosane 9E+06

7.6352 Cyclopentane, 1,2,3,4,5-pentamethyl- 9E+06

17.273 1,2-Benzisothiazole 9E+06

7.3178 2-Cyclopenten-1-one, 2-methyl- 9E+06

25.553 3,4-Dimethoxyphenylacetone 8E+06

42.483 Tetracosane 8E+06

30.884 Anthracene-D10- 8E+06

13.089 2-Bromo-2-nitropropane 7E+06

48.516 Octacosane 7E+06

8.5563 Octane, 3-methyl-6-methylene- 6E+06

21.022 Phenol, 2-methoxy-4-propyl- 6E+06

9.8101 Cyclotetrasiloxane, octamethyl- 6E+06

44.079 Pentacosane 6E+06

15.776 Creosol 5E+06

47.092 Heptacosane 5E+06

49.895 Hentriacontane 5E+06

23.028 Ethanone, 1-(3-hydroxyphenyl)- 5E+06

19.632 2-Methoxy-4-vinylphenol 5E+06

51.229 Hexacosane, 1-iodo- 5E+06

26.251 4-(1-Hydroxyallyl)-2-methoxyphenol 5E+06

30.536 Syringylacetone 4E+06

24.295 3,4-Dimethoxythiophenol 4E+06

12.726 p-Cresol 4E+06

31.552 6-Methoxychromanone 4E+06

11.469 2-Cyclopenten-1-one, 2,3-dimethyl- 4E+06

24.802 Hexathiane 4E+06

23.969 6-Methoxy-3-methylbenzofuran 4E+06

7.5653 Butyrolactone 4E+06

17.249 m-Guaiacol 4E+06

52.519 Heptacosane 3E+06

42.622 5-Octadecene, (E)- 3E+06

39.095 Heptacosane 3E+06

52.19 Clionasterol acetate 3E+06

10.389 1,3-Benzodioxole 3E+06

53.772 Hentriacontane 3E+06

8.8719 2(3H)-Furanone, dihydro-5-methyl- 3E+06

12.027 Phenol, 2-methyl- 3E+06

9.7347 Azetidine, 3-methyl-3-phenyl- 3E+06

12.456 Acetophenone 3E+06

8.7821 Octane, 3-methyl-6-methylene- 2E+06

28.337 7-Methoxy-1-naphthol 2E+06

75

7.7113 4-Propyl-2-hydroxycyclopent-2-en-1-one 2E+06

27.383 2-Butanone, 4-(4-hydroxy-3-methoxyphenyl)- 2E+06

10.107 2-Cyclopenten-1-one, 3,4-dimethyl- 2E+06

14.882 Benzene, 1,2-dimethoxy- 2E+06

14.926 1,2,4-Trithiolane, 3,5-dimethyl- 2E+06

16.038 2-Methoxy-5-methylphenol 2E+06

20.379 Piperonal 2E+06

34.149 5,10-Diethoxy-2,3,7,8-tetrahydro-1H,6H-dipyrrolo[1,2-a:1',2'-d]pyrazine

2E+06

7.4759 Ethanone, 1-(2-furanyl)- 2E+06

23.397 Phenol, 2-methoxy-4-propyl- 2E+06

14.684 1,2,4-Trithiolane, 3,5-dimethyl- 2E+06

13.209 Ethanone, 1-(2-thienyl)- 2E+06

24.582 Pyrolo[3,2-d]pyrimidin-2,4(1H,3H)-dione 2E+06

23.082 3,5-Dimethoxy-4-hydroxytoluene 2E+06

40.824 Octadecane, 2-methyl- 2E+06

18.049 1,2-Benzenediol, 3-methoxy- 2E+06

35.413 Hexadecane, 1-iodo- 2E+06

14.602 3-Oxobutan-2-yl (E)-2-methylbut-2-enoate 1E+06

15.267 Cyclobutanecarboxylic acid, 3,5-difluorophenyl ester 1E+06

10.365 Dihydro-2(3H)-thiophenone 1E+06

24.417 Benzaldehyde, 2,4-dihydroxy-3,6-dimethyl- 1E+06

31.576 3-Buten-2-one, 4-(4-hydroxy-3-methoxyphenyl)- 1E+06

55.05 Octacosane, 1-iodo- 1E+06

8.1096 2,5-Hexanedione 1E+06

16.284 Catechol 1E+06

7.9981 Heptane, 3-ethyl-5-methylene- 1E+06

15.637 o-n-Propylhydroxylamine 1E+06

25.656 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 1E+06

8.5995 3-Butene-1,2-diol, 1-(2-furanyl)- 1E+06

36.573 Disulfide, bis(4-methylphenyl) 1E+06

19.822 Carvenone 1E+06

11.035 1-(3H-Imidazol-4-yl)-ethanone 1E+06

23.338 Benzaldehyde, 3-hydroxy-4-methoxy- 1E+06

27.787 6-Methoxychroman-2-one 1E+06

29.648 2,6-Diisopropylnaphthalene 1E+06

6.5301 3-Ethyl-4-methyl-2-pentene 1E+06

27.915 3-pyridinecarbonitrile, 1,2-dihydro-2-imino-1-phenyl- 1E+06

27.01 2-(Methylmercapto)benzothiazole 9E+05

8.0579 2-Heptene, 5-ethyl-2,4-dimethyl- 9E+05

18.152 Phenol, 4-ethyl-2-methoxy- 9E+05

8.3267 2-Cyclopenten-1-one, 3,4-dimethyl- 9E+05

9.1555 2,5-Pyrrolidinedione, 1-(benzoyloxy)- 9E+05

11.264 Cyclobutane, 1,2-dipropenyl- 9E+05

19.521 Benzaldehyde, 2-hydroxy-3-methoxy- 9E+05

20.762 Phenol, 2-methoxy-4-(1-propenyl)- 9E+05

18.69 L-Alanine, N-L-alanyl- 9E+05

11.099 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- 8E+05

28.653 2,6-Diisopropylnaphthalene 8E+05

76

7.8305 Ethane, 1,1,2,2-tetrachloro- 8E+05

12.107 5-Methyl-3H-1,3,4-oxadiazole-2-thione 8E+05

7.1655 4,4-Dimethyl-2-oxazoline 8E+05

14.578 Cyclopentasiloxane, decamethyl- 8E+05

29.75 1-Naphthalenecarboxamide, N-(2-phenylethyl)-N-ethyl- 8E+05

12.219 2-Cyclopenten-1-one, 2,3,4-trimethyl- 7E+05

13.643 3-Ethyl-3-hexene 7E+05

49.768 3,4-Divanillyltetrahydrofuran 7E+05

28.476 2,6-Diisopropylnaphthalene 7E+05

35.124 Butyl myristate 7E+05

17.016 2-Acetyl-5-methylfuran 7E+05

26.066 4',6'-Dihydroxy-2',3'-dimethylacetophenone 7E+05

47.624 1,4-Benzenedicarboxylic acid, bis(2-ethylhexyl) ester 7E+05

29.532 2,6-Diisopropylnaphthalene 6E+05

32.191 Cyclo(L-prolyl-L-valine) 6E+05

12.061 2-Methylbutanoic anhydride 6E+05

19.915 3-Amino-4,6-dimethylpyridone-2(1H) 6E+05

26.561 Benzeneacetic acid, 4-(acetyloxy)-3-methoxy-, methyl ester 6E+05

25.423 Phenol, 2,5-bis(1-methylethyl)-, acetate 6E+05

17.782 1H-Imidazole-4-carboxaldehyde 6E+05

13.5 Succinic acid, 2-methylpent-3-yl pentafluorophenyl ester 6E+05

22.122 Phenol, 2-methoxy-4-(1-propenyl)-, acetate 6E+05

39.437 [1,1'-Biphenyl]-4,4'-diol, 3,3'-dimethoxy- 6E+05

18.267 1H-Benzimidazole, 5-methoxy- 5E+05

30.328 2-(1,1-Dimethylethyl)-6-(1-methylethyl)phenol 5E+05

10.243 1-(3H-Imidazol-4-yl)-ethanone 5E+05

22.54 Ethanone, 1-(2-hydroxy-6-methoxyphenyl)- 5E+05

10.185 2-Thiophenecarboxylic acid, 4-nitrophenyl ester 5E+05

25.008 2,5-Dihydroxy-4-methoxyacetophenone 5E+05

32.734 1H-Cyclopenta[b]quinoline-9-carboxylic acid, 2,3-dihydro- 5E+05

29.223 2,2,5,5-Tetramethyl-3-hexanone 5E+05

19.438 2,5(1H,3H)-Pentalenedione, tetrahydro-, cis- 4E+05

19.357 Cyclohexasiloxane, dodecamethyl- 4E+05

8.3775 1,2,4,5-Tetrazin-3-amine 4E+05

15.299 1,4-Benzenediol, 2-methoxy- 4E+05

14.314 1,2,4,4-Tetramethylcyclopentene 4E+05

33.744 d-Proline, n-butoxycarbonyl-, octyl ester 4E+05

31.388 Sulfurous acid, 2-ethylhexyl hexyl ester 3E+05

10.085 3(2H)-Thiophenone, dihydro-2-methyl- 3E+05

16.508 3,4-Hexanedione, 2,2,5-trimethyl- 3E+05

14.435 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone 3E+05

11.985 2-Cyclopenten-1-one, 2-hydroxy-3,4-dimethyl- 3E+05

40.321 Silane, diethylnonyloxypropoxy- 3E+05

19.981 2',6'-Dihydroxy-3'-methylacetophenone 3E+05

7.0191 2(3H)-Furanone, 5-methyl- 3E+05

8.9202 Dihydro-3-(2H)-thiophenone 3E+05

37.479 1H-isoindole-1,3(2H)-dione, 2-(5-methoxy-8-nitro-1-naphthalenyl)- 2E+05

13.257 2-Furancarboxylic acid, tetrahydro-3-methyl-5-oxo- 2E+05

52.402 Benzeneethanamine, .beta.-hydroxy-.alpha.-methyl-N-octadecyl- 1E+05

77

38.356 1,3-Benzenediol, o-methoxycarbonyl-o'-(2-furoyl)- 1E+05

49.206 Silane, dimethyl(4-methoxyphenoxy)pentadecyloxy- 6E+04

Table 33 - Sample 4Lo ordered from highest component area to lowest

Component RT Compound Name Component Area

13.029 Phenol, 2-methoxy- 2E+07

21.921 Vanillin 5E+06

6.1855 Methylene chloride 1E+06

24.122 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 1E+06

9.8663 Cyclotetrasiloxane, octamethyl- 4E+05

25.137 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)-

2E+05

9.6959 Phenol 2E+05

16.178 2-Methoxy-5-methylphenol 2E+05

20.628 Phenol, 2,6-dimethoxy-, acetate 2E+05

13.475 2,4-Dihydroxybenzaldehyde, 2TMS derivative 1E+05

14.582 Cyclopentasiloxane, decamethyl- 8E+04

29.659 3-Phenyl-4-hydroxyacetophenone 8E+04

28.668 2,6-Diisopropylnaphthalene 8E+04

30.905 Phenanthrene-D10 7E+04

29.763 Benzo[d,E]isocoumarin, 3,3-dimethyl- 7E+04

28.489 1,5-Diacetylnaphthalene 6E+04

29.545 1-Acetyl-4,6,8-trimethylazulene 6E+04

Table 34 - Sample 4L1 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.035 Phenol, 2-methoxy- 7E+07

21.927 Vanillin 3E+07

24.118 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)- 9E+06

6.1908 Methylene chloride 5E+06

25.138 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 3E+06

20.622 Phenol, 2,6-dimethoxy- 1E+06

16.172 Creosol 1E+06

9.6739 Phenol 8E+05

29.866 5'-Hydroxy-2',3',4'-trimethylacetophenone 6E+05

29.659 2,6-Diisopropylnaphthalene 4E+05

18.607 Phenol, 4-ethyl-2-methoxy- 4E+05

28.664 2,6-Diisopropylnaphthalene 4E+05

27.942 Homovanillic acid 3E+05

28.487 2,6-Diisopropylnaphthalene 3E+05

29.764 2,6-Diisopropylnaphthalene 3E+05

7.5693 4H-1,2,4-Triazol-4-amine 3E+05

29.544 2,6-Diisopropylnaphthalene 3E+05

10.381 1,3-Benzodioxole 2E+05

30.899 Phenanthrene-D10 2E+05

11.3 Cyclobutane, 1,3-diisopropenyl-, trans 1E+05

13.491 2,4-Dihydroxybenzaldehyde, 2TMS derivative 1E+05

20.396 Piperonal 1E+05

78

26.48 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 1E+05

8.5123 Methacrolein 1E+05

21.031 4-Hydroxybenzamide 1E+05

28.211 Phenethylamine, 3,4,5-trimethoxy-.alpha.-methyl-

1E+05

19.646 Ethanone, 1-(2-hydroxy-5-methylphenyl)- 9E+04

14.579 Cyclopentasiloxane, decamethyl- 9E+04

26.256 4-(1-Hydroxyallyl)-2-methoxyphenol 9E+04

17.314 Adenine 9E+04

23.974 Ethanone, 1-(2,3,4-trimethylphenyl)- 6E+04

25.566 Dimethyl-(isopropyl)-silyloxybenzene 6E+04

9.7195 Azetidine, 3-methyl-3-phenyl- 6E+04

14.434 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone

5E+04

28.795 .beta.-Carboline, 8-methoxy-1-methyl- 4E+04

28.351 7-Methoxy-8-aminoisoquinoline 4E+04

22.719 3-Acetyl-2,5-dimethylthiophene 4E+04

Table 35 - Sample 4L2 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.027 Phenol, 2-methoxy- 4E+07

21.921 Vanillin 1E+07

24.119 Ethanone, 1-(3-hydroxy-4-methoxyphenyl)-

3E+06

25.14 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)-

9E+05

6.1828 2-Pyrrolidinone, 5-(ethoxymethyl)- 7E+05

20.627 2,3-Dimethoxyphenol 5E+05

16.172 2-Methoxy-5-methylphenol 5E+05

9.6763 Phenol 4E+05

9.8824 Cyclotetrasiloxane, octamethyl- 4E+05

7.5638 1,2,4,5-Tetrazine, 1,4-dihydro-3,6-dimethyl-

2E+05

18.607 Phenol, 4-ethyl-2-methoxy- 2E+05

29.867 5'-Hydroxy-2',3',4'-trimethylacetophenone

1E+05

30.898 Phenanthrene-D10 1E+05

10.372 Glutaric acid, di(2-(4-fluorophenyl)ethyl) ester

7E+04

11.255 4-Vinyl-imidazole 5E+04

27.945 Homovanillic acid 5E+04

19.643 Ethanone, 1-(2-hydroxy-5-methylphenyl)-

5E+04

13.205 1H-Pyrazole, 5-methoxy-1,3-dimethyl- 3E+04

29.666 3-Phenyl-4-hydroxyacetophenone 2E+04

28.492 Benzo[d,E]isocoumarin, 3,3-dimethyl- 2E+04

29.536 3-Phenyl-4-hydroxyacetophenone 2E+04

79

Table 36 - Sample 4L3 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.027 Phenol, 2-methoxy- 3E+08

21.914 Benzaldehyde, 3-hydroxy-4-methoxy- 1E+08

24.109 Apocynin 6E+07

25.13 Guaiacol, 4-butyl- 3E+07

20.618 Phenol, 2,6-dimethoxy- 1E+07

16.167 Creosol 1E+07

9.6677 Phenol 9E+06

9.8653 Cyclotetrasiloxane, octamethyl- 7E+06

29.858 5'-Hydroxy-2',3',4'-trimethylacetophenone 4E+06

18.604 Phenol, 4-ethyl-2-methoxy- 4E+06

6.2678 Methylene chloride 3E+06

36.384 Cyclic octaatomic sulfur 2E+06

8.7402 Phenyl-pentamethyl-disiloxane 2E+06

17.288 Benzothiazole 2E+06

10.377 1,3-Benzodioxole 2E+06

11.275 D-Limonene 2E+06

7.5623 Cyclopentane, 1,2,3,4,5-pentamethyl- 1E+06

19.638 2-Methoxy-4-vinylphenol 1E+06

38.84 Hexadecanoic acid, butyl ester 1E+06

27.939 Homovanillic acid 1E+06

13.482 2,5-Dihydroxybenzaldehyde, 2TMS derivative 1E+06

20.393 Piperonal 1E+06

29.652 2,6-Diisopropylnaphthalene 1E+06

14.578 Cyclopentasiloxane, decamethyl- 1E+06

26.253 4-(1-Hydroxyallyl)-2-methoxyphenol 1E+06

30.894 Anthracene-D10- 1E+06

28.657 2,6-Diisopropylnaphthalene 9E+05

26.475 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 9E+05

8.5024 Pyrrolidine 9E+05

29.759 2,6-Diisopropylnaphthalene 9E+05

28.48 2,6-Diisopropylnaphthalene 8E+05

23.97 6-Methoxy-3-methylbenzofuran 8E+05

29.534 2,6-Diisopropylnaphthalene 8E+05

7.3119 2-Cyclopenten-1-one, 2-methyl- 7E+05

7.6454 Butyrolactone 7E+05

9.3452 4-Methyl-2H-pyran 7E+05

25.557 3,4-Dimethoxyphenylacetone 7E+05

21.026 Phenol, 2-methoxy-4-propyl- 6E+05

28.196 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 6E+05

29.793 4,5-Dimethoxy-2-hydroxyacetophenone 6E+05

24.803 Hexathiane 6E+05

11.481 2-Cyclopenten-1-one, 2,3-dimethyl- 6E+05

39.238 Oxalic acid, allyl octadecyl ester 5E+05

12.704 p-Cresol 5E+05

23.252 2-Butanone, 4-(4-hydroxyphenyl)- 5E+05

42.479 Tridecane, 2-methyl- 5E+05

80

9.704 Azetidine, 3-methyl-3-phenyl- 5E+05

24.122 2-Naphthyl methyl ketone 5E+05

42.254 Octadecanoic acid, butyl ester 5E+05

15.785 Phenol, 4-methoxy-3-methyl- 4E+05

45.607 Docosane, 1-iodo- 4E+05

24.302 Propane, 2-iodo- 4E+05

14.895 Benzene, 1,2-dimethoxy- 4E+05

22.976 3,6-Dimethyl-4H-furo[3,2-c]pyran-4-one 4E+05

8.911 2(3H)-Furanone, dihydro-5-methyl- 3E+05

48.513 Tetracosane, 1-iodo- 3E+05

9.8 3-Pentenoic acid, 4-methyl- 3E+05

27.351 3-Ethoxypyrazolo[3,4-d]pyrimidin-4(5H)-one 3E+05

19.364 Cyclohexasiloxane, dodecamethyl- 3E+05

14.423 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone

3E+05

7.9364 Octane, 3-methyl-6-methylene- 3E+05

6.4228 Norflurane 3E+05

12.461 Acetophenone 3E+05

27.019 2-(Methylmercapto)benzothiazole 3E+05

12.029 Phenol, 2-methyl- 3E+05

47.086 Tetracosane, 1-iodo- 3E+05

44.074 Dodecane, 1-iodo- 3E+05

25.427 5'-Hydroxy-2',3',4'-trimethylacetophenone 3E+05

24.59 benzoic acid, 4-hydroxy-3-propyl- 3E+05

49.891 Dodecane, 1-iodo- 2E+05

23.407 Phenol, 2-methoxy-4-propyl- 2E+05

51.227 Tetracosane, 1-iodo- 2E+05

39.098 Tetradecane, 1-iodo- 2E+05

30.543 Desaspidinol 2E+05

28.344 7-Methoxy-1-naphthol 2E+05

22.707 Phenol, 3,4-dimethoxy- 2E+05

13.194 3,3-Diisopropyl-N-methylazetidin-2,4-dione 2E+05

14.003 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone

2E+05

20.765 Phenol, 2-methoxy-4-(1-propenyl)-, acetate 1E+05

17.897 Benzaldehyde, 2,4-dihydroxy-6-methyl- 1E+05

16.047 Benzene, 1,4-dimethoxy- 1E+05

23.091 1,2,3-Trimethoxybenzene 1E+05

31.566 6-Methoxychromanone 1E+05

35.414 Sulfurous acid, 2-ethylhexyl hexyl ester 1E+05

27.796 D-Alanine, N-(4-anisoyl)-, undecyl ester 1E+05

52.519 Nonane, 5-methyl-5-propyl- 1E+05

19.802 4,5-Pyrimidinediamine 1E+05

28.782 Benzo[d,E]isocoumarin, 3,3-dimethyl- 1E+05

36.579 2-Fluorobenzoic acid, 4-methoxyphenyl ester 1E+05

15.274 Cyclobutanecarboxylic acid, 3,5-difluorophenyl ester 9E+04

16.706 3,4,5-Trifluorobenzyl alcohol, 2-methylpropyl ether 9E+04

14.685 1,3,5-Trithiocycloheptane 9E+04

18.698 L-Alanine, N-L-alanyl- 7E+04

81

40.821 2,4,7-Octanetrione 5E+04

42.62 1-Hexyne, 3-ethoxy-3,4-dimethyl- 5E+04

21.498 Silane, diethyloctadecyloxy(2-methoxyethoxy)- 5E+04

31.387 Octa-3,5-diene-2,7-dione, 4,5-dihydroxy- 5E+04

35.122 Ferrocene, acetyl- 3E+04

37.483 1H-isoindole-1,3(2H)-dione, 2-(5-methoxy-8-nitro-1-naphthalenyl)-

3E+04

Table 37 - Sample 4L4 ordered from highest component area to lowest

Component RT Compound Name Component Area

13.044 Phenol, 2-methoxy- 5E+08

21.926 Vanillin 3E+08

24.113 Apocynin 1E+08

25.132 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 9E+07

20.616 Phenol, 2,6-dimethoxy- 4E+07

16.167 Creosol 3E+07

9.6698 Phenol 2E+07

29.854 6-Methoxychromanone 2E+07

27.942 Benzenepropanol, 4-hydroxy-3-methoxy- 1E+07

18.604 Phenol, 4-ethyl-2-methoxy- 1E+07

29.652 2,6-Diisopropylnaphthalene 9E+06

6.2782 1-Buten-3-yne, 1-chloro-, (Z)- 9E+06

29.758 2,6-Diisopropylnaphthalene 7E+06

28.657 2,6-Diisopropylnaphthalene 7E+06

28.48 2,6-Diisopropylnaphthalene 6E+06

29.536 2,6-Diisopropylnaphthalene 6E+06

9.8841 Cyclotetrasiloxane, octamethyl- 4E+06

36.387 Cyclic octaatomic sulfur 4E+06

26.472 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- 4E+06

6.4264 1,2,4,5-Tetrazine, 1,4-dihydro-3,6-dimethyl- 4E+06

30.89 Anthracene-D10- 3E+06

7.5758 Cyclopentane, 1,2,3,4,5-pentamethyl- 3E+06

8.7448 3-Hydroxy-4-methoxybenzaldehyde, TBDMS 3E+06

28.191 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 3E+06

19.636 2-Methoxy-4-vinylphenol 3E+06

11.278 Cyclobutane, 1,2-dipropenyl- 2E+06

17.284 Benzothiazole 2E+06

9.7989 Cyclotetrasiloxane, octamethyl- 2E+06

26.252 4-(1-Hydroxyallyl)-2-methoxyphenol 2E+06

29.79 Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)- 2E+06

25.558 3,4-Dimethoxyphenylacetone 2E+06

38.842 Hexadecanoic acid, butyl ester 2E+06

9.2934 2-Cyclopenten-1-one, 3-methyl- 2E+06

7.2883 2-Cyclopenten-1-one, 2-methyl- 2E+06

21.027 Phenol, 2-methoxy-4-propyl- 2E+06

23.971 6-Methoxy-3-methylbenzofuran 2E+06

8.516 Pyrrolidine 2E+06

20.996 Benzaldehyde, 4-hydroxy- 2E+06

20.388 Piperonal 2E+06

82

39.241 Oxalic acid, allyl octadecyl ester 1E+06

11.476 2-Cyclopenten-1-one, 2,3-dimethyl- 1E+06

13.482 2,5-Dihydroxybenzaldehyde, 2TMS derivative 1E+06

14.578 Cyclopentasiloxane, decamethyl- 1E+06

15.783 Creosol 1E+06

24.805 Hexathiane 1E+06

24.299 3,4-Dimethoxythiophenol 1E+06

12.711 p-Cresol 1E+06

23.252 Phenol, 2-methoxy-4-(2-propenyl)-, acetate 1E+06

8.5534 Cyclohexane, 1-bromo-4-methyl- 1E+06

24.104 6-Methoxy-3-methylbenzofuran 1E+06

8.8937 2(3H)-Furanone, dihydro-5-methyl- 9E+05

42.482 Tetracosane, 1-iodo- 9E+05

9.7147 Azetidine, 3-methyl-3-phenyl- 9E+05

27.351 3-Ethoxypyrazolo[3,4-d]pyrimidin-4(5H)-one 8E+05

28.784 2,6-Diisopropylnaphthalene 8E+05

42.255 Octadecanoic acid, butyl ester 8E+05

45.61 Tetradecane, 1-iodo- 7E+05

12.46 Acetophenone 7E+05

28.341 7-Methoxy-1-naphthol 7E+05

7.4505 Ethanone, 1-(2-furanyl)- 6E+05

30.542 Desaspidinol 6E+05

12.029 Phenol, 2-methyl- 6E+05

23.403 Phenol, 2-methoxy-4-propyl- 6E+05

48.518 Hexadecane, 1-iodo- 6E+05

14.89 Benzene, 1,2-dimethoxy- 6E+05

24.132 2,4,6,(1H,3H,5H)-Pyrimidinetrione, 5-acetyl- 6E+05

23.036 Ethanone, 1-(3-hydroxyphenyl)- 6E+05

11.062 3-Furancarboxylic acid 6E+05

44.075 Dodecane, 1-iodo- 5E+05

31.555 Methanimidamide, N'-(3-methoxyphenyl)-N,N-dimethyl- 5E+05

13.198 Ethanone, 1-(2-thienyl)- 5E+05

25.426 Ethanone, 1-(2,3-dihydro-1,4-benzodioxin-6-yl)- 5E+05

47.088 Dodecane, 1-iodo- 5E+05

22.704 Phenol, 3,4-dimethoxy- 5E+05

14.616 2-Hepten-4-one, 2-methyl- 5E+05

27.793 6-Methoxychroman-2-one 5E+05

22.97 3',4'-(Methylenedioxy)acetophenone 5E+05

10.118 Ethanone, 1-(2-furanyl)- 5E+05

24.424 Benzaldehyde, 2,4-dihydroxy-3,6-dimethyl- 4E+05

24.589 Benzeneethanamine, N-[(3,4-dimethoxyphenyl)methyl]-3,4-dimethoxy-

4E+05

16.046 Phenol, 4-methoxy-3-methyl- 4E+05

39.099 Undecane, 3,8-dimethyl- 4E+05

49.895 Dodecane, 1-iodo- 4E+05

14.924 1,2,4-Trithiolane, 3,5-dimethyl- 4E+05

27.014 2-(Methylmercapto)benzothiazole 4E+05

23.09 3,5-Dimethoxy-4-hydroxytoluene 4E+05

19.361 Cyclohexasiloxane, dodecamethyl- 4E+05

83

8.3012 2-Cyclopenten-1-one, 3,4-dimethyl- 4E+05

14.429 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone 4E+05

12.217 2-Cyclopenten-1-one, 3,5,5-trimethyl- 4E+05

20.768 Phenol, 2-methoxy-4-(1-propenyl)-, (Z)- 4E+05

14.682 1,2,4-Trithiolane, 3,5-dimethyl- 3E+05

9.1394 Phenylglyoxylic Acid, 3-methylbutyl ester 3E+05

51.231 Hexadecane, 1-iodo- 3E+05

13.672 4-Hexen-3-one, 4-methyl- 3E+05

15.271 Cyclobutanecarboxylic acid, 3,5-difluorophenyl ester 3E+05

8.1613 2,5-Hexanedione 3E+05

14.007 4,6'-Dimethoxy-2'-(tert.-butyldimethylsilyl)oxychalcone 2E+05

12.915 1,2,4-Triazin-3-amine, 5,6-dimethyl- 2E+05

42.616 1,7-Dimethyl-4-(1-methylethyl)cyclodecane 2E+05

17.895 Benzaldehyde, 2,4-dihydroxy-6-methyl- 2E+05

13.377 2-Propen-1-amine, N,N-dipropyl- 2E+05

52.523 Dodecane, 1-iodo- 2E+05

18.278 1H-Benzimidazole, 5-methoxy- 2E+05

36.574 2-Fluorobenzoic acid, 4-methoxyphenyl ester 2E+05

19.444 2,5(1H,3H)-Pentalenedione, tetrahydro-, cis- 1E+05

40.824 Borane, diethyl(decyloxy)- 1E+05

25.011 2,5-Dihydroxy-4-methoxyacetophenone 1E+05

47.618 1,3-Benzenedicarboxylic acid, bis(2-ethylhexyl) ester 9E+04

21.5 Silane, diethyloctadecyloxy(2-methoxyethoxy)- 7E+04

37.479 1H-isoindole-1,3(2H)-dione, 2-(5-methoxy-8-nitro-1-naphthalenyl)-

6E+04

32.948 Isoparvifuran 5E+04

39.447 [1,1'-Biphenyl]-4,4'-diol, 3,3'-dimethoxy- 5E+04

50.74 Heptafluorobutyramide, N-(2-pentyl)-N-butyl- 5E+04

27.559 Terbutaline, N-trifluoroacetyl-O,O,o-tris(trimethylsilyl)deriv. 4E+04

Table 38 - Microalgae sample ordered from highest base peak area to lowest

Component RT Compound Name Base Peak Area Area %

7.5218 Pyrazine, 2,5-dimethyl- 3E+07 1E+01

10.374 Pyrazine, trimethyl- 2E+07 7E+00

10.411 Benzonitrile, 4-fluoro- 2E+07 6E+00

34.279 Cyclo(L-prolyl-L-valine) 1E+07 4E+00

13.038 Phenol, 2-methoxy- 1E+07 4E+00

12.743 Pyrazine, 3-ethyl-2,5-dimethyl- 1E+07 3E+00

34.219 DL-Alanine, N-methyl-N-(byt-3-yn-1-yloxycarbonyl)-, pentadecyl ester

1E+07 3E+00

7.2732 2-Cyclopenten-1-one, 2-methyl- 9E+06 3E+00

34.164 5,10-Diethoxy-2,3,7,8-tetrahydro-1H,6H-dipyrrolo[1,2-a:1',2'-d]pyrazine

9E+06 3E+00

32.014 2H-imidazole-2-thione, 1,3-dihydro-4-(2-methylpropyl)-

8E+06 3E+00

33.899 3,4-Diethoxy-3-cyclobutene-1,2-dione 7E+06 3E+00

7.6424 Pyrazine, ethyl- 7E+06 2E+00

10.269 Pyrazine, 2-ethyl-6-methyl- 7E+06 2E+00

7.6991 Pyrazine, 2,3-dimethyl- 7E+06 2E+00

84

33.959 Pyrrolo[1,2-a]pyrazine-1,4-dione, hexahydro-3-(2-methylpropyl)-

6E+06 2E+00

32.243 Cyclo(L-prolyl-L-valine) 6E+06 2E+00

21.924 Vanillin 4E+06 1E+00

9.7405 Phenol 4E+06 1E+00

13.297 2,5-Pyrrolidinedione, 1-methyl- 4E+06 1E+00

13.783 Propylphosphonic acid, fluoroanhydride, heptyl ester

3E+06 1E+00

14.152 1,5-Dioxaspiro[5.5]undecan-9-one, 3,3-dimethyl- 3E+06 1E+00

85

Appendix 5 – HTC operation full data sheet

Table 39 - First and second week of HTC experiments results

RUN Volume

recovered

(ml)

collected

water

sample

(ml)

Makeup

water

(ml)

hydrochar

mass

obtained

(g)

mass

lignin

input

(g)

Hydrochar yield

(%)

0 480 60 280 9.04 25.040 36.10

First

week

1 455 60 278 14.1 25.010 56.36

2 492 70 308 12.9 25.030 51.56

3 457 65 374 12.9 25.020 51.71 4 396 70 700 13.3 25.020 53.16

RUN Volume

recovered

(ml)

collected

water

sample

(ml)

Makeup

water

(ml)

hydrochar

mass

obtained

(g)

mass

lignin

input

(g)

Hydrochar yield

(%)

0 460 65 305 13.3 25.010 53.09

Second

week

1 495 70 275 12.5 25.083 49.89

2 470 65 295 12.4 25.076 49.52

3 530 65 235 12.9 25.015 51.67 4 Dried out 18.3 25.033 72.95

Table 40 - Third and fourth week HTC experiments results

RUN Volume

recovere

d (ml)

collecte

d water

sample

(ml)

Makeu

p water

(ml)

hydrocha

r mass

obtained

(g)

mass

lignin

input

(g)

Hydrocha

r yield (%)

0 490 65 275 11.93 25.032 47.66

Third

week

1 482 65 283 12.29 25.054 49.04

2 510 65 255 12.99 25.073 51.82

3 535 65 230 13.07 25.050 52.18 4 515 65 13.28 25.069 52.97

RU

N

Volume

recovere

d (ml)

collecte

d water

sample

(ml)

Makeu

p water

(ml)

hydrocha

r mass

obtained

(g)

mass

lignin

input

(g)

Hydrocha

r yield

(%)

0 490 70 280 12.13 25.020 48.49

Fourt

h

week

1 485 65 280 12.33 25.020 49.26

2 520 65 245 12.71 25.021 50.80

3 530 65 235 13.11 25.022 52.39 4 530 65 12.70 25.056 50.67

86

Appendix 6 – Guaiacol Quantification Data set

Table 41 - Concentration values after recovery and dilution normalization

Conc real

1L0 0.138 mg/ml

1L1 1.17 mg/ml

1L2 1.06 mg/ml

1L3 1.30 mg/ml

1L4 4.51 mg/ml

2L0 1.06 mg/ml

2L1 2.64 mg/ml

2L2 1.59 mg/ml

2L3 21.7 mg/ml

3L0 0.405 mg/ml

3L1 1.11 mg/ml

3L2 0.603 mg/ml

3L3 0.282 mg/ml

3L4 0.798 mg/ml

4L0 34.9 mg/ml

4L1 10.6 mg/ml

4L2 23.1 mg/ml

4L3 2.09 mg/ml

4L4 1.57 mg/ml

87

Figure 4 - Guaiacol concentration values plot to observe the patterns

0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

40.00

1 2 3 4

Co

nce

ntr

atio

n (

mg/

ml)

Week

Guaiacol concentration calculated over the recycling

Run 0 Run 1 Run 2 Run 3 Run 4

88