Emissions of volatile organic Karin Granström compounds from Emissions of volatile wood organic compounds from wood Division for Engineering Sciences, Physics and Mathematics Department of Environmental and Energy Systems

The central aim of this thesis is to support the efforts to counteract certain environ- mental problems caused by emissions of volatile organic compounds. The purpose of this work was (1) to develop a method to measure emissions from dryers, (2) to determine the effect of drying medium temperature and end moisture content of the processed material on emissions of monoterpenes and other hydrocar- Karin Granström bons, (3) to examine the emissions of monoterpenes during production of pellets, and (4) to examine the natural terpene emissions from forests with an eye to implications for modelling. The measurement method (1) resolves difficulties caused by diffuse emissions and high moisture content of the drying medium. The method as used here has an uncertainty of 13% using a 95% confidence interval. Emissions of volatile organic Emissions from a continuous spouted bed (2) drying sawdust at 140°C, 170°C or 200°C were analysed. When the sawdust end moisture content was reduced below 10%wb, emissions of terpenes and VOC per oven dry weight increased rapidly. Higher compounds from wood drying medium temperature also increased emissions. Examination of sawdust and wood pellets from different pellets producers (3) re- vealed that most of the terpene emissions happened during the drying step. Using sawdust with higher moisture content in the pellets press increased terpene emissions. Factors affecting terpene emissions from tree species in Sweden were reviewed (4). Implications for models of atmospheric chemistry and carbon budgets are discussed.

Karlstad University Studies Karlstad University Studies ISSN 1403-8099 2005:6 ISBN 91-85335-46-0 Karin Granström

Emissions of volatile organic compounds from wood

Karlstad University Studies 2005:6 Karin Granström. Emissions of volatile organic compounds from wood.

Dissertation

Karlstad University Studies 2005:6 ISSN 1403-8099 ISBN 91-85335-46-0

© The author

Distribution: Karlstad University Division for Engineering Sciences, Physics and Mathematics Department of Environmental and Energy Systems SE-651 88 KARLSTAD SWEDEN +46 54-700 10 00 www.kau.se

Printed at: Universitetstryckeriet, Karlstad 2005 The branches of my brain are alive to sun and rain my forest mind is in tune with the wind there is reason in my resin

Kenneth White, Mahamudra

3

Summary

The central aim of this thesis is to support the efforts to counteract certain environmental problems caused by emissions of volatile organic compounds.

The purpose of this work was (1) to develop a method to establish the amount of emitted substances from dryers, (2) to determine the effect of drying medium temperature and end moisture content of the processed material on emissions of monoterpenes and other hydrocarbons, (3) to examine the emissions of monoterpenes during production of pellets, and (4) to examine the natural emissions from forests with an eye to implications for modelling.

The measurement method (1) resolves the difficulties caused by diffuse emissions, and also solves the problems associated with high moisture content of the drying medium. The basic idea is to use water vapour to determine the exhaust flow, and to use a dry ice trap both to preconcentrate emitted VOCs and to determine the moisture content of the drying medium. The method, as used in this paper, has an uncertainty of 13% using a 95% confidence interval.

Emissions from a spouted bed (2) in continuous operation drying Norway Spruce sawdust at temperatures of 140°C, 170°C or 200°C were analysed with FID and GC-MS. When the sawdust end moisture content was reduced below 10%wb, emissions of terpenes and of total VOC per oven dry weight increased rapidly. The increased temperature of the drying medium entering the drying tower also caused an increase in the amounts of emitted monoterpenes at sawdust moisture contents below the fibre saturation point.

Examination of sawdust and wood pellets from different pellets producers (3) revealed that most of the terpene emissions take place during the drying step, with flue gas dryers causing higher emissions than steam dryers. Almost all of the volatile terpenes remaining in wood after drying were released during pelleting. Increased terpene emissions during the pelleting process were found when sawdust with a higher moisture content was used.

Terpenes emitted naturally from vegetation can have adverse environmental impacts. Factors affecting terpene emissions from tree species in Sweden were reviewed (4). Models for prediction of terpene fluxes should include not only temperature but also light intensity, seasonal variation, and a base level of herbivory and insect predation. Prediction of high concentrations of ambient terpenes demand sufficient resolution to capture emission peaks, e.g., those caused by bud break.

5

Sammanfattning

Avhandlingens centrala mål är att bidra till att motverka de miljöproblem som uppstår vid utsläpp av lättflyktiga organiska ämnen (VOC). Fokus har legat på terpener, en typ av VOC som bildas av träd och finns i kåda. Höga koncentrationer av terpener uppstår främst vid bearbetning av trä, exempelvis vid torkning av sågspån och vid senare processteg som tillverkning av träpellets.

Delmål var att (1) utveckla en metod att mäta utsläpp av VOC och terpener från ångtorkar, (2) klarlägga hur mängden och koncentrationen av VOC, samt mängden och sammansättningen av däri ingående terpener, ändras med torktemperatur och materialets slutfukthalt, vid kontinuerlig torkning av sågspån i fluidiserad bädd med recirkulerande torkmedium, (3) undersöka avgången av terpener från olika typer av spåntorkar och vid tillverkning av träpellets, och (4) sammanställa och analysera det nuvarande kunskapsläget om naturliga emissioner av terpener för att se hur underlaget för dagens atmosfärskemiska modeller kan förbättras.

Den mätmetod (1) som utvecklats och testats löser kända problem vid mätning av kolväteutsläpp från torkar; t.ex. att det sker betydande läckage av torkgas från torken och att det höga fuktinnehållet i torkgasen stör mätutrustningen. Med ett konfidensintervall på 95% har metoden, som den används här, en mätnoggrannhet på 13%.

Emissionerna vid torkning (2) av sågspån från gran till olika slutfukthalter vid tre temperaturer (140°C, 170°C och 200°C) analyserades med FID och GC-MS. Vid torkning till fukthalter under ca 10% (vatten/totalvikt) ökade terpenavgången per torrsubstans snabbt. Med ökad temperatur på torkgasen in till torktornet ökar emissionerna när spånens slutfukthalt är under fibermättnadspunkten.

Analyser av sågspån och pellets från olika pelletsproducenter (3) visade att större delen av monoterpenerna avgår vid torkningen. Trumtorkar ger större emissioner än ångtorkar. De terpener som finns kvar i sågspånet efter torkningen försvinner till stor del vid pelletstillverkningen. En högre fukthalt på sågspånet i pelletspressen ger större emissioner.

Den naturliga avgången av terpener (4) blir ett problem om de kommer i kontakt med förorenad luft. Atmosfärskemiska modeller kan förbättras genom att ta hänsyn till faktorer som ljusmängd, variation över året, och skador från betande djur och insekter. Upplösningen i tid ska fånga lokala emissionstoppar, exempelvis vid lövsprickning.

7 Preface

When I studied to Master of Science in chemical engineering at Lund Institute of Technology, I became interested in toxicology, which led to an interest in environmental issues. Pursuing this interest, I combined my graduation project with studies in Human Ecology at Lund University. Finding this topic interesting but lacking in practical applications, I turned to studies in Environmental and Energy Systems. This led to PhD studies in Environmental and Energy Systems at Karlstad University.

I began my work as a PhD Student in 1999, and gyrated to the newly established research group in Bioenergy. This group studied energy efficiency in sawdust drying. I took up a related track by studying how the drying of sawdust could be done with a minimum of hydrocarbon emissions. We then worked together to investigate emissions from the production of pellets. The Bioenergy group has grown steadily, and it has been a pleasure to contribute in forming a strong research group.

Biofuels have an important role to play in the Scandinavian energy market. By analysing a potential environmental problem with the production of biofuels, and point to possible solutions, I seek to contribute to this development.

8 List of publications

This thesis is based on the following Papers, referred to in the text by their Roman numerals:

I . Granström KM. A method to measure emissions from dryers with diffuse leakages, using evaporated water as a tracer. Drying Technology 21(7):1197-1214, 2003.

II. Granström KM. Emissions of monoterpenes and VOC during drying of sawdust in a spouted bed. Forest Products Journal 53(10):48- 55, 2003.

III. Ståhl M, Granström KM, Berghel J, Renström R. Industrial Processes for Biomass Drying and Their Effects on the Quality Properties of Wood Pellets. Biomass and Bioenergy 27:621-628, 2004.

IV. Granström KM. A method to measure emissions from dryers with diffuse leakages II. Sensitivity studies. To be published in Drying Technology, issue 5, volume 23, 2005.

V. Biogenic emissions of monoterpenes in Sweden — a review with implications for modelling. Submitted to Atmospheric Environment.

Results relating to this thesis are also presented in:

Granström KM. Utsläpp av lättflyktiga kolväten vid torkning av biobränslen (eng: Emissions of volatile hydrocarbons (VOC) during drying of sawdust). Värmeforskrapport 745, Stockholm, 2001.

Granström KM. Emissions of volatile organic compounds during drying of wood. Karlstad University Studies 2002:14. Karlstad, 2002.

9 Results relating to this thesis have been reported at the following conferences:

Granström, K.M. Emissions of Monoterpenes and VOC during Drying of Sawdust in a Continuous spouted bed. Proceedings from the 12th European Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection, Amsterdam, the Netherlands, 17- 21 June, 2002.

Ståhl, M; Granström, K.M.; Berghel, J; Renström, R. Industrial Processes for Biomass Drying and their Effects on the Quality Properties of Wood Pellets. Proceedings of the first World Conference on Pellets, Stockholm, Sweden, 2-4 September, 2002. pp 87-91.

Granström, K.M. Ny ångtorkningsteknik i mellanstor skala. Documentation from Pellets 2003, Lundsbrunn, Sweden, 4-5 February, 2003. pp 25-26.

Granström, K.M. Steam Drying of Sawdust for Pellets Production. Proceedings from the International Nordic Bioenergy Conference and Exhibition, Jyvästylä, Finland, 2-5 September, 2003. pp 476-479.

Granström, K.M. A Method to Measure Emissions from Dryers with Diffuse Leakages. Proceedings from PRES’03 - 6th Conference on Process Integration, Modelling and Optimisation for Energy Saving and Pollution Reduction, Hamilton, Ontario, Canada, 26-29 October, 2003.

Results not included in this thesis have been reported at the following conference:

Granström, K.M. Reduced VOC Emissions from Birch Sawdust Dried in a Steam Dryer. Proceedings from CSChE 2003 - 53rd Canadian Chemical Engineering Conference, Hamilton, Ontario, Canada, 26-29 October, 2003.

10 Table of Contents

SUMMARY...... 5

SAMMANFATTNING...... 7

PREFACE ...... 8

LIST OF PUBLICATIONS ...... 9

TABLE OF CONTENTS ...... 11

1. INTRODUCTION...... 13

1.1. BACKGROUND ...... 13 1.2. OBJECTIVES OF THIS STUDY...... 14 1.3. FOCUS...... 15 2. EXTRACTIVES IN WOOD AND RELATED ENVIRONMENTAL ISSUES ...... 16

2.1. EXTRACTIVES IN WOOD ...... 16 2.2. ENVIRONMENTAL EFFECTS OF EMISSIONS OF MONOTERPENES...... 18 2.3. ATMOSPHERIC CHEMISTRY OF MONOTERPENES...... 19 2.4. ANTHROPOGENIC EMISSIONS OF MONOTERPENES...... 21 2.4.1. Anthropogenic emissions from logging...... 21 2.4.2. Anthropogenic emissions from storing of wood chips...... 21 2.4.3. Anthropogenic emissions from industrial barking...... 22 2.4.4. Anthropogenic emissions from sawing...... 22 2.4.5. Anthropogenic emissions from pulp and paper production ...... 23 2.4.6. Anthropogenic emissions from drying and pelleting...... 23 2.5. BIOGENIC PRODUCTION AND EMISSION OF MONOTERPENES...... 23 2.6. TOXICOLOGY OF MONOTERPENES ...... 25 2.7. COMMERCIAL PRODUCTS FROM TERPENES...... 26 3. DRYING OF WOOD...... 27

3.1. METHODS OF INDUSTRIAL DRYING...... 27 3.2. VOC EMITTED DURING DRYING ...... 28 3.3. WOOD CHARACTERISTICS IMPORTANT FOR EMISSIONS DURING DRYING ...... 29 3.3.1. Temperature in the wood during drying ...... 30 3.3.2. Mechanisms of terpene release during drying of sawdust ...... 30 3.4. RELATED WORK ON EMISSIONS DURING DRYING ...... 31 3.5. RELATED WORK ON EMISSIONS DURING PELLETS PRODUCTION ...... 33 4. EXPERIMENTS ...... 34

4.1. MATERIAL ...... 34 4.2. DRYER ...... 34 4.3. ANALYTICAL EQUIPMENT ...... 36 4.4. CALCULATIONS ...... 38 4.4.1. Concentration of monoterpenes ...... 39 4.4.2. Concentration of volatile organic compounds...... 39 4.5. VALIDATION AND SENSITIVITY ANALYSIS...... 39 5. RESULTS AND DISCUSSION...... 40

5.1. MEASUREMENT METHOD [PAPER I AND IV]...... 40 5.2. EMISSIONS DURING DRYING OF SAWDUST [PAPER II] ...... 41 5.3. EMISSIONS OF MONOTERPENES FROM PELLETS PRODUCTION [PAPER III] ...... 42 5.4. BIOGENIC EMISSIONS OF TERPENES [PAPER V]...... 43

11 6. CONCLUSIONS ...... 44

7. FURTHER RESEARCH NEEDS...... 45

8. ACKNOWLEDGEMENTS...... 46

APPENDIX I. CHEMICAL AND PHYSICAL DATA OF MONOTERPENES ...... 47

APPENDIX II. SYMBOLS AND ABBREVIATIONS...... 48

REFERENCES...... 49

12 1. Introduction

1.1. Background

The use of biofuels has increased considerably over the last years in

Sweden. Environmental taxes on CO2 and NOx have made biofuels cost- competitive to other energy sources. Biofuels have further advantages over fossil hydrocarbons: (1) they do not emit net CO2 to the atmosphere, (2) they are a renewable resource and (3) they create local job opportunities.

The drying of wood-based biofuels is important since the moisture content is one of the most important criteria of quality (Berghel and Renström, 2004). During storage of wet wood, fungal particles that have been shown to cause health problems will increase. Wet wood also results in low combustion temperatures, which lead to low energy efficiency and high emissions of hydrocarbons and particles. If biofuels are dried and compressed to pellets or briquettes, the fuel will have controlled moisture content and higher energy density, and it will be easier to transport and take up less room during storage.

Extractives in wood are emitted during drying and pelleting. This is a cause of environmental problems. The emitted wood extractives, volatile organic compounds (VOC), contribute in the presence of nitrogen oxides and sunlight to the formation of photo-oxidants. The photo-oxidants are harmful to humans, as they cause irritation in the respiratory tract and in sensitive parts of the lungs. They also disturb photosynthesis, causing damage to forests and crops. The major part of the VOCs emitted to air during drying are monoterpenes (Johansson and Rasmuson, 1998).

Anthropogenic emissions of biogenic VOCs primarily come from wood processing in forestry and the forest industry. Anthropogenic emissions occur due to machining, logging, chipping, drying, debarking, sawing and pulping. Such point emissions can create high concentrations of photo- oxidants locally. However, there are also large natural emissions of biogenic VOCs from trees and other plants. These emissions are dominated by monoterpenes, isoprene and volatile carbonyl compounds.

Antropogenic and biogenic monoterpene emissions are interconnected. Increased biogenic production will increase the monoterpene content in wood, which will translate into increased emissions during the logging, barking and processing of wood.

13 1.2. Objectives of this study

This study was made to improve the environmental performance and the resource use efficiency of biofuel systems. Specifically, the purpose was to investigate emissions of volatile hydrocarbons during drying and pelleting in order to decrease environmental and health hazards. In addition, the natural emissions of monoterpenes have been examined.

The aim of the first paper was to establish a method to measure diffuse emissions from dryers with recirculating drying medium [Paper I]. This was followed by a thorough sensitivity analysis [Paper IV].

The experiments described in the second paper investigate the monoterpene and VOC emissions from the drying of Norway Spruce sawdust in a continuous spouted bed [Paper II]. The main objective of this paper was to determine how the temperature of the drying medium and the final moisture content of the processed material affect the total amount, composition, and drying medium concentration of VOC emitted during drying.

In a related study, the emissions of monoterpenes and VOC during drying of Scots Pine sawdust were investigated. In addition, the energy use during drying to different moisture contents at different temperatures was examined. The results, together with the data in Paper II, were published in a report (Granström, 2001).

The third paper broadens the view from the drying of sawdust to encompass the production of pellets. The aim was to determine the fate of the monoterpenes left in sawdust after drying, when the dried sawdust is used for pellets production.

In paper V, the biogenic emissions of monoterpenes are investigated, and implications for modelling studies are discussed.

14 1.3. Focus

In this study, the focus has been on emissions of monoterpenes. Compounds I believe to be sesquiterpenes and diterpenes have been detected in emissions from wood processing, but since monoterpenes were clearly the dominant group, the non-monoterpene compounds were not identified, nor quantified. The analysis method employed for identification of compounds is not suitable for some of the highly volatile compounds that have been found in emissions from several wood species. These substances include formic acid, acetic acid, formaldehyde, acetaldehyde and methanol. While these substances were not individually identified, the total amount of emitted hydrocarbons was detected using another method of analysis.

The material used in the drying experiments reported in Paper II was sawdust of Norway Spruce. It should be noted that the amount and composition of emissions are species specific.

15 2. Extractives in wood and related environmental issues

2.1. Extractives in wood

The amount and composition of extractive organic compounds in wood depend on species of tree, time of year, tree genetics and age, and vary within individual plants.

The extractive organic compounds in wood can be classified into three groups based on their role in plant physiology:

1. nutrient reserve; 2. plant hormones; 3. protective and wood conserving substances.

The nutrient reserve is made up of fatty acids and fats. The most abundant fatty acids are linoleic acid, oleic acid and linolenic acid. Fatty acids are usually esterised with glycerol to fat, which is found in cells in marrow streaks. The amount of fat is highest in autumn and lowest in spring. Plant hormones are sterols, a group of compounds closely related to triterpenes. Substances with protective and wood conserving properties are terpenes, resin acids, phenols and tannic acids.

The terpenes are found in resin. In sapwood of both conifers and hardwoods, resin is located in parenchyma cells or resin canals. Parenchyma resin consists of terpenes, esters, fats and waxes. The resin in resin canals is composed of resin acids dissolved in volatile terpenes. In conifer heartwood, resin is distributed throughout the tissue (Back, 2002b).

In conifers, the terpene group consists mostly of mono- sesqui- and diterpenes, whereas triterpenes and sterols dominate in deciduous trees (Fengel and Wegener, 1984; Sjöström, 1981).

The extractive organic compounds can also be classified into groups according to their chemical structure: terpenes and terpenoids, aliphatic compounds (fat, fatty acids, fatty alcohols and alkanes), and phenols (tannic acids, flavonoids, stilbenes).

16 Terpenes are defined as hydrocarbons built from isoprene units. Isoprene has the molecular structure CH2=C(CH3)-CH=CH2, and its formal name is 2-methyl-1,3-butadiene. Terpenes have the chemical formula (C5H8)n, where n≥2. They are classified according to the number of isoprene units per molecule, see table 2.1.

Table 2.1. Types of terpenes. Number of 23468>8 isoprene units: Classification mono- sesqui- di- tri- tetra- poly- terpene terpene terpene terpene terpene terpene

Monoterpenes (C10H16) are the most volatile group of the components present in wood. They are therefore of particular interest in studies of emissions from wood and from trees. The boiling points of monoterpenes are in the range of 150°C to 180°C. The chemical properties of monoterpenes are to a large degree dependent on the number of olefinic double bonds in the molecular structure. Monoterpenes can be acyclic, monocyclic or bicyclic, with three, two or one double bond, respectively. The molecular structures of some common monoterpenes are depicted in figure 2.1. The boiling points of sesquiterpenes are about 100°C higher than for monoterpenes.

α-pinene β-pinene myrcene 3-carene limonene

Figure 2.1. Molecular structure of some common monoterpenes.

The most abundant Swedish conifers, Norway Spruce and Scots Pine, have resin consisting to 25-30% of monoterpenes. Sesquiterpenes make up a few percent of the resin (Strömvall and Petersson, 1999). A rough estimate of the monoterpene content in wood is 0.1-0.15% of the tree’s dry substance for Norway Spruce and 0.2-0.6% for Scots Pine (Nussbaum and Englund, 1997). The terpene content in Norway Spruce is dominated by α-pinene, followed by β-pinene and 3-carene (often in an approximate relation of 3:2:1). In Scots pine, α-pinene and 3-carene dominate, followed by β-pinene.

17 2.2. Environmental effects of emissions of monoterpenes The most important environmental effects of monoterpene emissions are due to the formation of photo-oxidants. The photo-oxidants created due to monoterpene emissions cause forest and crop damage, and they are harmful to humans as they cause irritation in the respiratory tract and in sensitive parts of the lungs. For the general public, the smell around wood-processing units is likely to be the most noticeable environmental effect.

The concentration of monoterpenes in emission plumes caused by anthropogenic activities is typically 10-1000 times higher than the background level in conifer forests. Due to the short atmospheric lifespan of monoterpenes, the highest photo-oxidant concentrations can be expected within 5 hours after the emission takes place, and within a distance of 50 km (Strömvall and Petersson, 1999).

The rate-limiting initial reaction step during the daylight formation of photo-oxidants from monoterpenes generally involves reaction with a hydroxyl radical (OH-radical, HO•) (Atkinson et al., 1986) or with ozone (O3) (Atkinson and Carter, 1984). Monocyclic and noncyclic monoterpenes normally react more rapidly with ozone than with hydroxyl radicals. For the bicyclic monoterpenes, the two reactions compete; they generally react with OH-radical during the day, while at night the OH-radical concentration in ambient air is low and reactions with ozone and NO3-radical take over (Corchnoy and Atkinson, 1990).

The reactions between monoterpenes and ozone initially lower the ozone levels. However, in the presence of nitrogen oxides (NOx) and sunlight, net formation of ozone will follow. Emissions of nitrogen oxides in combination with terpenes increase ozone levels considerably. The ozonolysis of monoterpenes also gives rise to immediate formation of radicals, aldehydes, peroxides and other potentially harmful photo- oxidants (Hatakeyama et al., 1989; Hooker et al., 1985; Yokouchi and Ambe, 1985). Monoterpenes react more rapidly with both the OH-radical and O3 than most other hydrocarbons. This means that monoterpenes cause elevated concentrations of photo-oxidants faster and within shorter distances from the source than do most other hydrocarbons. During spring and summer days, when the formation of photo-oxidants is at its highest, the average atmospheric residence time of bicyclic monoterpenes may be less than one hour, and that of myrcene less than 10 minutes (table 2.2).

18 Table 2.2. Lifetimes of monoterpene molecules in ambient air (Altshuller, 1983). Southern Sweden is 55°N. July Midday July Average Jan Midday Summer 25-45°N 55°N 55°N at night Daylight Daylight Daylight Night Lifetime Lifetime Lifetime Lifetime (min) (h) (h) (h) α-pinene 36 1.4 3.8 1.5 β-pinene 66 4.6 14.0 6.3 3-carene 36 1.6 4.4 1.8 limonene 12 0.3 0.8 0.3 β-phellandrene 24 1.1 3.0 1.2 myrcene 6 0.2 0.4 0.2

Interactions with other emissions are important for the environmental impact of monoterpene emissions. If co-emitted with nitrogen dioxide

(NO2) and ozone (O3), the reaction rates of monoterpenes increase and organic nitrates may form (Kotzias et al., 1990). Sulphur dioxide (SO2) is oxidised more quickly in the presence of ozone and monoterpenes (Stangl et al., 1988). Terpenes are thus contributing to acid deposition and soil acidification, when co-emitted with NO2 and SO2.

Anthropogenic terpene emissions are usually emitted to air close to other process emissions. In the kraft and pulp industries, the terpene emissions are mixed with large emissions of both sulphur dioxide and nitrogen oxides (Strömvall and Petersson, 1992). The mechanical pulp industries co-emit considerable amounts of nitrogen oxides. Harvesters and other diesel machines used in forestry, as well as traffic on nearby roads, emit nitrogen oxides.

2.3. Atmospheric chemistry of monoterpenes

The relation between volatile organic compounds, NOx and ozone represents one of the major scientific challenges associated with urban air pollution (Sillman, 1999). A highly simplified set of reaction paths is included here as background. For a thorough review of gas-phase terpene oxidation products, see (Calogirou et al., 1999).

19 In the atmosphere, NO2 can absorb light and break up into a nitric oxide (NO) and a free excited (*) oxygen atom (reaction I). The free oxygen atom is very reactive and immediately combines with an oxygen molecule

(O2) to form ozone (reaction II). Ozone is also very reactive, and decomposes when it encounters nitric oxide (reaction III). The net reaction is no net change.

NO2 + light NO + O* I O* + O2 O3 II ↔ O3 + NO NO2 + O2 III no net reaction

When terpenes and other hydrocarbons (R-H) react with OH-radical or ozone, the reaction products can react further and form many different radicals (•) and oxidised radicals. An example is reaction IV and V (Petersson, 1997), where OH-radical reacts with VOC to form alkyl radical (R•) (IV), and the alkyl radical reacts with molecular oxygen to form alkyl peroxy radical (R-OO•) (V). Peroxy radicals can convert NO to NO2 (reaction VI).

R-H + HO• R• + H2OIV R• + O2 R-OO• V R-OO• + NO NO2 + RO• VI R-H + HO• + O2 + NO H2O + NO2 + R-O•

When nitric oxide reacts with peroxy radicals (HOO• and ROO•) instead of with ozone, the result is a net formation of ozone. The reactions above can be summarised as a sequence of two reactions:

↔ NO2 + O2 O3 + NO I , II R-H + HO• + O2 + NO H2O + NO2 + R-O• IV, V, VI R-H + HO• + 2O2 H2O + R-O• + O3

The excess ozone reacts with a NO radical during night-time, when the lack of UV-light hinders further decomposition of NO2.

20 2.4. Anthropogenic emissions of monoterpenes All machining, tooling and shaping of biomass is likely to cause monoterpene emissions. Drying is an important source of anthropogenic emissions of monoterpenes. Other activities that cause anthropogenic emissions include logging, chipping, debarking, sawing, pulping, and board production. It is important to know the magnitude of anthropogenic emissions in order to model effects on local atmospheric chemistry, assess the suitability of different process procedures, and see where efforts should be focused in order to decrease emissions.

2.4.1. Anthropogenic emissions from logging Forestry has a considerable impact on monoterpene emissions. Concentration levels in air for monoterpenes emitted during forestry operations in Southwest Sweden have been measured to 1.0-1.5 mg/m3 near the harvester during logging of both Scots Pine and Norway Spruce (Strömvall and Petersson, 1991). Above fresh branch wood, the corresponding levels were 100-500 µg/m3. Four weeks after thinning, the vegetation still emitted increased amounts of terpenes, the concentration in air being 50 µg/m3. This should be compared with the background level of 1 µg/m3. A pre-commercial thinning in a Ponderosa Pine plantation in the Sierra Nevada mountains, removing half of the biomass, gave a tenfold increase in monoterpene fluxes (Schade and Goldstein, 2003). A factor 2 increase in monoterpene emissions is sufficient to raise local tropospheric ozone production and suppress local hydroxyl radical concentrations (Litvak et al., 1999). Logging operations can therefore be suspected of altering regional atmospheric chemistry for a considerable time.

2.4.2. Anthropogenic emissions from storing of wood chips

Wood chips in heaps outdoors in a temperature of 12 °C have been shown to emit hydrocarbons, with stirring of the heaps having a noticeable effect (table 2.3) (Axelsson et al., 1992). A fan blowing at the heaps had an evaporative effect even after three weeks.

21 Table 2.3. Emissions from outdoor heaps of wood chips (mg C/m3) (Axelsson et al., 1992) Immediate Ten Minutes Twenty Minutes Effect after Stirring after Stirring Freshly cut Spruce 100 30 15 Spruce twelve hours after cutting 20 8 50% Norway Spruce, 50% Scots Pine 72 three weeks after cutting

A German study found an initially rapid decrease in terpene content in wood cut to chips, with the terpene content decreasing by 4% in a week, and a subsequently slower decrease (Marutzky, 1979) (table 2.4).

Table 2.4. Decreasing terpene content in wet and dry wood chips during storage (Marutzky, 1979). Storage Time Wet Wood Chips Dried Wood Chips (months) Terpenes in wood Terpenes left Terpenes in wood Terpenes left (g/kg odw) (%) (g/kg odw) (%) 0 4.8 100 0.7 100 4 1.327 0.47 67 8 0.67 14 0.343 12 0.49 10 0.26 37

If logging residues are stored uncomminuted, in covered windrows or in bundles, the risks of self-ignition and allergic reactions are eliminated and dry matter losses minimal (Jirjis, 1995). If logging residues are forwarded into a windrow directly after felling, and immediately covered with impregnated paper, the substance losses are less than 1% of the dry matter per month (Jirjis and Theander, 1990). The moisture content in bundles of newly harvested logging residues stored 9 months in windrows decreased from 43%wb to 26%wb when covered and to 30% when stored uncovered.

2.4.3. Anthropogenic emissions from industrial barking The concentration of monoterpenes in air during single-log barking of timber have been measured to 5-20 mg/m3, and during drum barking of pulpwood to 50-100 mg/m3 (Strömvall and Petersson, 1993a). Measurement of VOC in a drum barker during debarking of Spruce gave the average emission of 53 g per m3 of produced chips (Svedberg and Paulsson, 1995).

2.4.4. Anthropogenic emissions from sawing Measurements in Swedish sawmills have shown terpene concentrations of 50-550 mg/m3 in air (Lundberg, 1987). The higher concentrations were found in older studies before working conditions had received much attention.

22 In the production hall of a sawmill, the average emission of terpenes during sawing has been measured to 153 g/m3 of board for Pine and 25 g/m3 of board for Spruce (Svedberg and Paulsson, 1995).

Measurements of the monoterpene concentration in air at sawmills have shown large seasonal variability, at least when reasonably fresh wood is sawn (Conners et al., 2001). This has been attributed to seasonal variations in the monoterpene content in wood.

2.4.5. Anthropogenic emissions from pulp and paper production The sulphate pulp process gives turpentine as a by-product. Turpentine that was recovered from digester relief gases amounted to 2.5 kg per tonne sulphate pulp in 1991 (Strömvall and Petersson, 1993b). Sulphate pulp is mostly produced from Scots Pine. Depending on the wood used and the extent of turpentine recovery, Strömvall and Petersson estimated terpene emissions to be 0.6-5 kg/tonne sulphate pulp (Strömvall and Petersson, 1993b).

In the stone groundwood process, using Norway Spruce wood, monoterpene concentrations of more than 0.5 mg/m3 have been measured at ground level (Strömvall and Petersson, 1990). Released monoterpenes are often vented to air without recovery, despite that approximately 0.9 kg turpentine per tonne dry pulp can be recovered from process emissions (Strömvall and Petersson, 1999).

Efforts to recover turpentine have increased in recent years, but there is still more to be done.

2.4.6. Anthropogenic emissions from drying and pelleting This is discussed in chapter 3.

2.5. Biogenic production and emission of monoterpenes

Terpenes have several protective functions in plants (Kesselmeier and Staudt, 1999). They neutralise ozone that would disturb photosynthesis. They repel many insects and herbivores. They also lower the viscosity of resin, making it possible for resin to flow to a damaged part of the plant. There the volatile terpenes are emitted to air and non-volatile components of the resin are left as a hydrophobic cover, protecting the tree from further damage.

23 Monoterpenes are produced by the melalon acid pathway, starting with

Acetyl-CoA. They are made from two C5-units, isopenthyl-pyrophosphate and dimethylallyl-pyrophosphat, giving the C10-unit geranyl- pyrophosphat, which enzymes from the class monoterpene-cyclases transform in several steps to monoterpene hydrocarbons C10H16 (Gershenzon and Croteau, 1992; Goodwin and Mercer, 1983).

The content of monoterpenes in conifers of different species varies. Within the same species, the content varies between different tree stands and within individual trees. The terpene concentration in trees is known to vary seasonally. This seasonal cycle can be explained with plants adjusting their investment of resources in terpene- and terpenoid production to obtain sufficient protection against insects and herbivores without too great a drain on the plants’ resources (Lerdau et al., 1994).

Monoterpenes provide both constitutive and inducible defences. Constitutive defences are always present in a level dependent on genotype and resource availability. Terpene production has been shown to be affected by the availability of resources (e.g. biologically available nitrogen and water) and the plants’ growth stadium (Lerdau et al., 1995). Seasonal variation is also characterised by changes in terpene composition (Janson, 1993; Staudt et al., 2000). Monoterpene production is induced when the plant is attacked, for example, by herbivores, fungi, or insects (Gershenzon and Croteau, 1991; Raffa, 1991). When the plant is damaged, it produces substances that increase monoterpene syntase activity and thus terpene concentration. The terpenes that are normally present in small amounts increase the most. Therefore, the composition of monoterpenes change in response to external elicitors such as herbivore or pathogen attacks (Raffa, 1991). This implies that the terpenes that are normally present only in small amounts are those that most efficiently deter from attacks.

Terpenes and terpenoids are more expensive to synthesise per gram than most other primary and secondary metabolites. This is due to several factors: (1) their production necessitates extensive chemical reduction, (2) the enzyme costs of making terpenoids are high since terpenoid biosynthetic enzymes are apparently not shared with other metabolic pathways (plant cells may even have more than one set of enzymes for catalysing the steps of terpenoid production), and (3) the energy expended for storage is likely to be substantial since terpenoids are harmful for non- specialised plant cells and usually stored in complex multicellular specialised storage and secretory structures within the plant (Gershenzon, 1994).

24 2.6. Toxicology of monoterpenes

Exposure limits set by Swedish authorities for monoterpenes and turpentine are 25 ppm (150 mg/m3) on average over an eight-hour workday, and 50 ppm (300 mg/m3) over a fifteen minute period (AFS, 2000).

The toxic effects on humans of monoterpenes described in the scientific literature are primarily a result of simultaneous exposure to several different monoterpenes. This is the case, for example, in sawmills or during contact with turpentine. During experiments with exposure to terpenes in exposure chambers no acute toxicological effects have been demonstrated (Falk et al., 1991; Falk et al., 1990). However, it has long been known that exposure to wood dust during the processing of wood causes respiratory difficulties and irritation to mucous membranes (Ruppe, 1929). This has been confirmed in several later studies (Dahlqvist et al., 1992; Dahlqvist et al., 1996; Eriksson et al., 1997; Eriksson et al., 1996; Halpin et al., 1994a; Hedenstierna et al., 1983; Malmberg et al., 1996). Work related exposure to terpenes in air has been reported to cause problems in the respiratory tract at concentrations of 100-200 mg/m3 (Levin, 1994). Sawmill workers have an increased number of cells in the nasal mucous membrane and an increased reactivity in the respiratory tract (Eriksson et al., 1996; Halpin et al., 1994b), which indicates an acute toxicological effect. Exposure to sawmill fumes has also been shown to cause an acute decrease in carbon monoxide lung diffusing capacity (Eriksson et al., 1996). It was assumed that these problems were caused by terpenes or micro-organisms (Dahlqvist and Ulfvarson, 1994). However, as wood dust causes irritative effects not observed during exposure to terpenes, it has been suggested that the problems could be caused by oxygenated terpenes formed during the processing of wood or by terpenes reaching the lungs through adsorption to particles of wood dust (Malmberg et al., 1996). It could also be the dust particles themselves that cause the problems (Dahlqvist et al., 1996). Terpene oxidation products have been found to cause an increase in the sensitivity of the respiratory tract and a decrease in the lungs’ gas exchange ability (Malmberg et al., 1996).

Turpentine can cause allergic and non-allergic contact dermatitis (Cronin, 1979). Terpenes can form alkyl hydroperoxides (R-OOH), which are known to cause allergies and give a delayed oversensibility of the skin (Matura et al., 2003). Monoterpenes’ potential to cause irritative symptoms in mice depends on the molecules’ stereochemistry: (+)-pinenes

25 and (+)-carene have a similar irritative effect, while (−)-β-pinene is one quarter as irritating and (−)-α-pinene hardly irritating at all (Kasanen et al., 1999). Turpentine consists of a mixture of monoterpenes and has an irritative effect similar to that of (+)-pinene, why it can be concluded that turpentine’s irritative effects originate from its content of (+)-monoterpenes (Kasanen et al., 1999).

Monoterpenes do not differ regarding uptake, distribution or elimination. Inhalation causes a body uptake of 60-70% of the monoterpenes. Terpenes are stored in fatty tissue, which means that they have a long half-life. However, they are quickly metabolised by the enzyme system Cytochrome P-450. A few percent exits the body unchanged (Falk- Filipsson, 1995).

Terpenes are detectable by smell at low concentrations, the threshold for α-pinene is 16 µg/m3.

2.7. Commercial products from terpenes

Conifer terpenes are sold as turpentine and pine oil. Turpentine is a by-product from pulp production and is used as solvent in paints. The composition of terpenes in turpentine varies with tree species and type of pulp process. α-pinene and β-pinene are used as components of camphor, perfume and insect deterrent. Limonene-based solvents for cleaning and degreasing have been introduced as replacements for chlorinated solvents like trichloroethene and CFCs.

26 3. Drying of wood

3.1. Methods of industrial drying

There are many different types of dryers. A common ground for classification is the manner in which the heat is supplied to the material. This can be done in three different ways:

1. Convection: here the drying medium flows across the surface of the processed material and carries away the moisture. Convection dryers are also called direct dryers. In a rotary dryer, the processed material moves with or against the gas flow through a rotating pipe. In a belt dryer, the drying medium flows through the material that rests on a moving conveyor belt. In a fluidised bed dryer, the drying medium has high enough velocity to cause the processed material to float and the gas-solid mixture to behave like a fluid. In a flash dryer, the velocity of the drying medium is so high that the processed material is taken along, and transported through a series of pipe lengths and bends before being separated from the drying medium. A grinding dryer is a flash dryer with a mill grinder in the gas duct. The mill grinder serves to reduce the size of the processed material.

2. Conduction: here heat is supplied through heated surfaces and the moisture is carried away by a vacuum operation or by a flow of gas whose main function is to remove moisture. Conduction dryers are also called indirect dryers. In a paddle dryer and a screw dryer the processed material is transported through a tunnel with heated surfaces. Rotary dryers and flash dryers can be designed for indirect heating. (The heat transfer is partly due to convection also in conduction dryers).

3. Radiation: here heat is supplied by electromagnetic radiation with wavelengths ranging from microwave to the solar spectrum. Dryers using IR-radiation from electric elements are the most common kind.

Traditional drying media are flue gas and air. Superheated steam is an alternative that has attracted increased interest due to its larger potential for energy recovery. When the drying medium is flue gas or air, the evaporated moisture is mixed with combustion gases and air.

27 Condensation then occurs at relatively low temperatures, typically at 45-55°C. If the steam is not diluted, steam drying results in a condensate of higher and more useful temperatures.

During drying in direct dryers, terpenes follow the used drying medium out of the dryer. The drying medium is often led to an incinerator, where the terpenes are combusted. Flue gas recycling is favourable both in terms of emission control and in terms of energy efficiency. In an indirect dryer, terpenes will be found in the inert gases and can easily be combusted. If the drying medium is condensed, significant amounts of monoterpenes can be found as a separate phase on the condensate and may thus be recovered (Strömvall and Petersson, 1999). In the absence of solubility enhancing surfactants, terpenes are unlikely to be found in the condensate due to their low water solubility (appendix I).

3.2. VOC emitted during drying

During drying of wood, both volatile and less volatile compounds can be emitted to air, the latter by steam distillation. The volatile compounds emitted are primarily monoterpenes. The less volatile compounds include fatty acids, resin acids, diterpenes and triterpenes. The less volatile compounds emitted during drying have high boiling points, but sufficiently high vapour pressure to leave wood at 180-220°C. Less volatile compounds can be found as vapours in the drying medium, as aerosols or at the surface of particles (Bridgwater et al., 1995). When gaseous less volatile compounds leave the dryer, they cool in the surrounding air and condense to form small droplets called sub-micron aerosols. If the water vapour does not condense, the aerosols are visible as a blue haze. This mostly happens during drying at high temperatures.

During high temperature drying, thermal degradation of wood gives rise to formic acid, acetic acid, alcohols, aldehydes, furfurals and carbon dioxide (Bridgwater et al., 1995; Fengel and Wegener, 1984; Münter et al., 1999). It has not been established how high the temperature has to be before thermal degradation products are formed. Broege et al. gives 130°C as an estimate (Broege et al., 1996), whereas Bridgwater et al. report 200°C (Bridgwater et al., 1995). The temperature necessary to cause thermal degradation is likely to be somewhat dependent on the species of tree that is being dried. Degradation of emitted hydrocarbons in recirculating drying medium is probably dominated by gas phase reactions close to heating surfaces.

28 3.3. Wood characteristics important for emissions during drying

In general outline, the drying of hygroscopic materials, such as wood, proceeds in three stages (Fyhr and Rasmuson, 1996; Mujumdar and Menon, 1995). During the first stage, the wood contains free moisture and has a wet surface maintained by rapid capillary fluid transport. The drying rate is characterised by the evaporation of free water, and it is constant over time (when the bulk vapour pressure in the drying medium and the turbulent conditions are constant). The second stage occurs when dry spots appear on the surface of the drying material, at the critical moisture content. The movement of water is here characterised by mass diffusion, and the drying rate falls. The third stage begins when the surface film of moisture is completely evaporated. Moisture bound by absorption is removed and the drying rate is controlled by the net diffusion of water from the bulk of the processed material to its surface.

Moisture in wood occurs as free water in the cell lumen and as bound water in the cell walls. When the wood moisture content is above the fibre saturation point, the cell walls are saturated and excess water is found in the lumen.

Trees have two distinct types of wood, sapwood and heartwood. Sapwood of both softwoods and hardwoods is porous with continuous channels for water, nutrients and resin. These different channels are in softwoods, but not in hardwoods, connected through pores. Pines have a developed resin canal system. Norway Spruce has regular resin channels only in the bark, although traumatic resin channels and resin pockets develop as a response to wounding and mechanical stress (Back, 2002a). In the heartwood of softwoods, large amounts of adhesives seal the apertures and break off water transport (Bengtsson and Sanati, 2004b). Also, the lumen is filled with extractives and resin is found throughout the tissue (Back, 2002a).

During drying of conifers, the pits in sapwood aspirate successively, to be mostly sealed when the moisture content falls below the fibre saturation point. In conifer heartwood, moisture is bound within the cell walls, causing a reduced drying rate. This means that the transport of water is very different in sapwood and heartwood above the fibre saturation point, whereas, below the fibre saturation point, heartwood and sapwood are similar where water transport is concerned (Bengtsson and Sanati, 2004b).

29 3.3.1. Temperature in the wood during drying

During drying, the temperature in wood chips first increases to the boiling point of water at the applied pressure. Then, at about 10%wb wood moisture content, the wood temperature rapidly increases to match the drying medium temperature (Johansson and Rasmuson, 1998).

Differences in the wood structure, e.g., permeability, cause the temperature in the middle of the chip to remain at the boiling point for a longer period of time in Pine than in Spruce. In addition, the increase in temperature from the boiling point to the temperature of the drying medium is faster in Pine than in Spruce (Danielsson and Rasmuson, 2002).

3.3.2. Mechanisms of terpene release during drying of sawdust

Studies of VOC emissions over time during batch drying of softwoods have shown a high initial peak, followed by linear decrease, and then a broad peak that begins when the wood is almost dry (Banerjee et al., 1995; Ingram et al., 2000; Karlsson, 2001). The intensity of the second signal increases with increasing dryer temperature, with a sharp increase above the boiling point of α-pinene. This indicates that the emissions from dry wood is driven by vapour pressure (Banerjee et al., 1998).

At least three mechanisms are operative for the movement and release of α-pinene and other terpenes from wood particles (Banerjee, 2001). An initial burst of α-pinene very early in the drying process is mainly attributed to the loss of α-pinene dissolved in surface water. Then, α- pinene and water are released in a near-constant ratio. The similar emission profiles indicate a common mechanism, probably that water mobilises α-pinene from the interior of the sawdust particle, as surfactants present in wood solubilise α-pinene into water. Finally, α-pinene is emitted through evaporation when the wood is almost dry.

This mechanism of terpene release have been shown to apply also to commercial drying of lumber (Conners et al., 2002). The first emission burst was independent of temperature, suggesting that it originated from surface material when the wood heated. Then α-pinene and water were released in a ratio of approximately 1:1000. Finally, in the falling rate phase, monoterpene emissions increased as the water emissions tapered off.

30 3.4. Related work on emissions during drying

There are several published studies dealing with the problem of emissions of monoterpenes and other VOC from wood during drying, see examples in table 3.1. In some more recent work, e.g., (Danielsson and Rasmuson, 2002), (Johansson, 2002), (McDonald et al., 2002), (NCASI, 2002), (Bengtsson and Sanati, 2004a), either only one monoterpene is measured or the units used are incompatible with the ones in table 3.1.

Reports of monoterpene emissions from the drying of wood sawdust, chips and lumber range from (<10)-740 mg/kg odw for Norway Spruce, 210-2020 mg/kg odw for Scots pine, 120-200 mg/kg odw for Radiata pine, 210-315 mg/kg odw for Douglas-fir, to 817-1590 mg/kg odw for Ponderosa Pine (table 3.1).

In the studies referred to, the focus of interest has generally been on presenting information about the total emission of VOC during drying of boards. This is because much research has been motivated by environmental regulations (USA) on VOC emission from dryers, and boards are the most common form of wood to be dried. However, there are also studies on the effects of different drying parameters of VOC emissions from sawdust.

Important parameters mentioned for emissions released are the species of tree, drying temperature, drying time, initial moisture content and the size of the processed material.

It is evident that tree species differ in the amount of monoterpenes emitted during drying, cf. table 3.1. In a Swedish context, it is especially interesting that Scots Pine emits considerably more monoterpenes during drying than does Norway Spruce (Broege et al., 1996; Englund and Nussbaum, 2000; Granström, 2003).

Drying of wood fragments and sawdust often gives higher emission values than drying of boards, cf. table 3.1. The generally higher emissions from the drying of sawdust are likely due to shorter diffusion paths and use of different types of dryers using higher temperatures.

If the difference between initial and final moisture content is large, more drying is required and more emissions of VOC can be expected (Wu and Milota, 1999).

31 Table 3.1. Emissions of VOC during drying of wood as measured in the exhaust gas. – indicates no information. Tmax=maximum temperature of the drying medium. MCend=end moisture content of the dried wood.

References Tree Dimension Tmax (°C) Mono- Other VOC of Wood terpenes (mg/kg odw) th; w; l (mm) (mg/kg odw) sawdust and chips (Ek et al., 2000) – sawdust 450-500 440 (Englund and Norway fragments 60 740 Nussbaum, 2000) Spruce (Englund and Scots pine, fragments 60 500-860 Nussbaum, 2000) heartwood (Englund and Scots pine, fragments 60 840-2020 Nussbaum, 2000) sapwood (Granström, 2003) Norway sawdust 140 10-50 (end MC ≈10%) Spruce " " " 170 20-90 " " " 200 70-140 (Karlsson, 2001) Scots pine sawdust 160 3500-5000 (Münter et al., – sawdust 550-600 505-865 356-768 1999) Boards and timber (Broege et al., Norway 24;–;– 60 50 10 1996) Spruce " " 60;–;– 66 <10 <10 (Broege et al., Scots pine 30; –;– 65 380 50 1996) " " 50; –;– 66 210 10 (Ingram et al., Southern 50;150;610 115 10-1500 1995) pine (Ingram et al., Southern timber 82 2700 1996) pine " " " 118 2600 (Lavery and Milota, Douglas-fir 41;165; – 210 790 2000) (lab scale) 1120 (Lavery and Milota, " 41;165;– – 315 870 2000) (commercial drier) (Lavery and Milota, Ponderosa 40;120-300 – 817 1490 2001) (lab scale) pine ;1120 (Lavery and Milota, " 40;120-300 – 1590 2210 2001) (commercial ;4900 drier) (McDonald and Radiata pine 35;205;600 120 120 110 Wastney, 1995) " " " 140 200 180 (Shmulsky, 2000) Southern lumber 150 600-2300 pine (Wu and Milota, Douglas-fir 42;147; 93 790 1999) 1245

32 The results of earlier studies differ regarding the effect of the drying temperature on the amount of VOC emitted per oven dry weight (odw). For example, McDonald and Wastney (1995) report 60-70% larger VOC emissions when drying with air at 140°C than at 120°C, whereas Ingram et al. (1996) noticed no difference in VOC emissions when drying at 82°C and 118°C, although emissions per unit of time were larger at the higher temperature. Banerjee (2001) found the total amount of α-pinene to increase with increasing temperature, in the examined temperature interval 105-200°C, and suggests there may be occluded regions in the wood from which α-pinene can not be removed by water but are emitted as terpene vapour.

During drying of hardwood chips, a sharp rise in VOC concentration has been observed when the wood moisture content falls below 10%. This has been attributed to thermal wood degradation causing emissions of methanol and aldehydes. Increasing the final flake moisture by a few percent reduces the period of exposure of the dry wood to high temperature, and leads to a decrease in VOC emissions. Removal of fines also reduces VOCs, since the fines tend to over-dry (Su et al., 1999).

3.5. Related work on emissions during pellets production

No studies quantifying terpene emissions during the production of pellets have been found. The available research has a working environment perspective, focusing on the concentration in the pellet plants.

In a terpene exposure study of six Swedish pellet producers, the workers’ personal exposure to monoterpenes ranged from 0.64 to 28 mg/m3 (Edman et al., 2003).

In another study, two pellet plants that use dried raw material had a peak terpene concentration in air of 23 mg/m3 and 15 mg/m3, respectively, and one pellet plant using non-dried sawdust in the pellet press had as much as 119 mg/m3 in one spot (Davila, 2002).

These studies of terpene concentrations in pellet plants show the concentration in air and the workers’ personal exposure to be below the exposure limits of 150 mg/m3 set by the Swedish authorities. However, the plant in the Davila study, using sawdust with high moisture content, came rather close to the exposure limits. This suggests that changes in the process towards using drier sawdust may be advantageous.

33 4. Experiments

4.1. Material

Norway Spruce (Picea abies) was used in the experiments described in paper I and II, since it is a very common wood processed in the sawmill industry in Sweden. In addition, sawdust from Scots Pine (Pinus sylvestris) was used in experiments published in a report (Granström, 2001).

The sawdust was taken fresh from a sawmill located 5 km from the dryer, transported and stored in sacks of woven polypropylene at room temperature, and used for tests within a week. The sawmill processes timber grown in the region, in central Sweden. Sawdust was taken with a shovel from a large outdoor heap formed under the operating saw blade. Both Norway Spruce and Scots Pine are sawn at the mill. To avoid collecting mixtures of sawdust from different tree species, sawdust was collected after at least two hours of sawing of the same tree species.

The materials used for the experiments described in paper III were samples from five pellets producers, and sawdust before and after drying in the KaU dryer. All pellets producers used dried material in the pellet press. Three pellet producers supplied samples of wet and dry sawdust as well as pellets. Dried wood, dried material and pellets were examined from the pellets producers that use raw material from lumber. All the pellet assortments had a diameter of 8 mm. Three of the pellets producers use sawdust as raw material, two also use cutter shavings. The sawdust and cutter shavings used for pellet production originate from Norway Spruce, Scots Pine or both.

After the publication of paper III, materials from a sixth pellet producer were obtained, i.e., wet and dry sawdust and pellets. The sawdust had been dried in a rotary drum dryer with flue gas; the outlet temperature was 130°C.

4.2. Dryer

A continuous spouted bed dryer with recirculating drying medium was used. The dryer works under atmospheric pressure.

34 The spouted bed dryer consisted of six key components: fan, heater, drying tower, cyclone, feeding screw, and vent (figure 4.1). The sawdust was transported from a container to the drying tower with the feeding screw and fed down the top of the drying tower where it met a stream of superheated steam. The processed material stayed circulating in the drying tower and was in this way dried until it was pneumatically transported into the cyclone. There, the sawdust was separated from the gas flow and collected in a sack of woven polypropylene. The drying medium was led to the fan, heated by the heater and then returned to the drying tower. The sawdust continuously gave off water vapour. To offset an increase in pressure in the system, drying medium was released through the vent when the overpressure exceeded 100 Pascal.

Cold trap

Temperature T2 FID

Temperature T3 Material inlet

Cyclone Vent Drying tower

Fan

Pressure Pressure drop 2 drop 1

Material outlet

Temperature T1 Flow meter Heater

Figure 4.1. Schematic illustration of the spouted bed dryer used in the drying experiments. The picture is modified from (Berghel and Renström, 2002). The positions of temperature sensors 1-3 and the differential pressure sensors 1-2 are indicated, as well as the equipment for VOC measurements. The drying tower was 2 meters high, had a diameter of 0.3 meter, and a cone angle of 20° measured from the median. The diameter of the inlet duct was 0.10 meter.

35 At the time of the experiments reported in paper II, the moisture content of the dried sawdust was controlled by three parameters: the temperature of the drying medium that enters the drying tower (T1), the amount of material in the spouted bed, and the flow of drying medium.

The drying medium was heated to 140°C, 170°C or 200°C. The amount of material in the spouted bed was measured as pressure drop over the drying tower and set to values between 250 and 750 Pa. The flow of drying medium was measured as the pressure drop over a restriction and generally set to 180 to 220 Pa (0.131 to 0.145 m3/s).

When the sawdust used for paper III was dried, the control system had been rebuilt to let the moisture content of the dried sawdust be controlled by the temperature after the drying tower. For details on the new control system, see (Berghel and Renström, 2004).

4.3. Analytical equipment

The concentration of VOC in the drying medium was measured continuously with a Total Hydrocarbon Analyser with a Flame Ionisation Detector (FID). The FID was used to confirm steady-state conditions and to observe the variation of the total amount of volatile hydrocarbons in the drying medium with various drying parameters.

Identification and quantification of emitted substances were accomplished using a Gas Chromatograph with a Mass Spectrometric detector (GC-MS). A dry ice trap was used both to preconcentrate emitted VOCs and to determine the moisture content of the drying medium.

Soxhlet extraction was used for the validation of the cold trap method as well as for the analysis of terpene content in pellets and samples of sawdust described in paper III.

The FID used was a J.U.M VE7. It was calibrated with a test gas of 900 ppm methane, and thus it measured the concentration of hydrocarbons in the drying medium as methane equivalents. These data have subsequently been transformed to monoterpene equivalents to facilitate comparisons with GC-MS data.

36 In a gas chromatograph, a sample’s components are separated into pure compounds. The separated compounds are then transferred to the mass spectrometer, where each compound fragments in a unique pattern, shown as a mass spectrum. The separation of the monoterpenes is shown in figure 4.2.

Figure 4.2. Gas chromatographic separation of substances detected in emissions from the drying of Spruce. Scan compound 77 α-pinene

87 camphene

106 β-pinene

116 myrcene

136 3-carene

150 p-cymene

155 limonene

231 γ-terpinene

Identification of the monoterpenes was made both from their retention time (their time in the capillary column), and from their mass spectrum.

Drying medium was led through a heated pipe to the cold trap, a flask placed in dry ice at -78°C, where water and hydrocarbons formed a solid. The trapping system is shown in figure 4.3. Dichloromethane was added when a test-run was complete. The dichloromethane phase was then analysed with GC-MS.

The concentration of monoterpenes in the drying medium was calculated from the amount of monoterpenes in the dry ice trap and the flow of dry air through the pump.

37 4.4. Calculations

The amount of emitted terpenes and total VOC during the run was calculated as the volume of the drying medium emitted times the concentration of terpenes and total VOC in the drying medium, respectively.

Since the drying medium re-circulates, the exhaust gas flow volume flow could not be determined using the set flow rate. Instead, it was calculated from the weight of water evaporated from the processed sawdust, and the concentration of water vapour in the drying medium. With knowledge of the total amount of water added to a volume of gas, and the resulting concentration of water in the gas, the amount of gas could be calculated.

For the unit operation of drying, water was added to the dryer in the form of moisture in the processed material. This moisture either left the dryer in the outgoing processed material, or was vaporised during drying. Water vapour was thus added to the drying medium. The weight of vaporised water was calculated from the weight loss of the processed material during drying, the drying time, and the amount of sawdust dried. The volume of water vapour dried off from sawdust during a run was then calculated using the ideal gas law.

Sample flow; drying gas

T T Dry air

Pump

Flask

Sublimate

Dry ice Figure 4.3. The cold trap system.

The moisture content of the drying medium was calculated using data from the dry ice trap (fig 4.3). When the sample flow of drying gas reached the trap, the water and VOCs in the gas were retained in the flask. The air in the drying gas continued to the pump. The weight of the

38 condensate in the dry ice trap was used to calculate the volume of water vapour that had entered the flask, using the ideal gas law. The volume of dry air that had entered the flask was measured after the dry ice trap. Then the volume percentage of water vapour in the drying medium could be determined.

The total gaseous volume of kiln emissions was calculated as the volume of water vapour emitted to the drying medium divided by the volume percentage of water vapour in the drying medium.

4.4.1. Concentration of monoterpenes

The weight concentration of terpenes in the drying medium was calculated as the weight of terpenes in the cold trap, divided by the volume of drying gas that had been pumped through the trap. The amount of terpenes emitted was determined as drying medium concentration of terpenes times volume of drying medium used. This was then related to the amount of dry substance that was processed.

4.4.2. Concentration of volatile organic compounds

The concentration of VOC in the drying medium in terms of mg monoterpenes per cubic meter gas was calculated using the proportion of VOC in the drying medium as ppm and the ideal gas law. The total amount of VOC emitted was then calculated as mg per kg oven dry weight.

4.5. Validation and sensitivity analysis

Two kinds of tests were made to establish the reliability of the measurement method in paper I.

A series of experiments were made in which known amounts of one of the detected substances, β-pinene, were mixed with a small amount of sawdust and added to the dryer. The extra amounts of β-pinene were detected to 91-98%.

In addition, the monoterpene content of sawdust before and after drying was analysed with Soxhlet extraction. The emissions, as determined with Soxhlet extraction, were close to those determined with the method in paper I. Individual compounds registered to 65-104%, with the exception of p-cymene, which was not at all detected with Soxhlet.

39 5. Results and Discussion

5.1. Measurement method [paper I and IV]

A novel method to measure emissions from dryers with diffuse emissions has been developed and tested [paper I]. The method resolves the known difficulties caused by diffuse emissions and solves the problems associated with the high moisture content of the drying medium. The basic idea is to use water vapour to determine the exhaust flow, while a dry ice trap is used both to preconcentrate emitted VOCs and to determine the moisture content of the drying medium. To estimate the experimental uncertainties, four runs were made using the same drying parameters. Those experiments had a standard deviation of 36 mg/kg.

For one of these experiments, a sensitivity analysis was made, as described in paper IV. It showed that the terpene emission per oven dry weight ± (terpodw) was 254 47 mg/kg using a 99% confidence interval. With a 95% ± confidence interval, terpodw was 254 33 mg/kg. The uncertainty was therefore almost 19% using a 99% confidence interval; and 13% with a 95% confidence interval.

It is a common rule of thumb that the maximum theoretical error equals three times the standard deviation of actual experiments (as approximately 99.7% of the values lie within ±3 standard deviations of the mean). Assuming a 99% confidence interval as the maximum theoretical error, this would give the terpodw in the experiment in paper IV a standard deviation of 16 mg/kg.

As the standard deviation from uncertainties of the measurement method (16 mg/kg) is smaller than the standard deviation from a series of experiments (36 mg/kg), conclusions can be drawn about the difficulties in reproducing an experiment. The uncertainty in the measurement method does not overshadow the variations underlying other experimental factors. Known sources of variation are the facts that different sawdust are dried at each experiment (even if the same batch is used, there is internal variation and a time differential), and that MCout has to be estimated (e.g., using the measured drying tower temperature) since it cannot be measured during drying. The sensitivity analysis described in paper IV can be used to increase the robustness of the results by increasing the precision, or to decrease costs for analysis by avoiding measuring with unnecessary exactness.

40 5.2. Emissions during drying of sawdust [paper II]

The final moisture content of the processed material is a very important factor for emissions of VOC from the drying process. Emissions are also influenced by the temperature of the drying medium entering the drying tower (T1) at the temperature intervals used in this study.

Emissions per oven dry weight (odw) of terpenes and VOC increased rapidly when the sawdust moisture content was reduced below 10% (water/total weight). This was shown for monoterpenes using GC-MS and for VOC using FID.

The total VOC concentration in the recirculating drying medium, however, was not affected by the sawdust’s final moisture content. Nor was the composition of different monoterpenes in the drying medium influenced in a consistent way by the final moisture content of the sawdust.

An increase in the temperature of the drying medium entering the drying tower caused a larger emission of monoterpenes at moisture contents below the fibre saturation point. In addition, the relative amount of less volatile monoterpenes increased, as did the total VOC concentration in the drying medium.

The total monoterpene content, as well as the composition of monoterpenes, varied between different processed materials. The steam condensate did not contain any detectable amounts of monoterpenes at the drying parameters used.

41 5.3. Emissions of monoterpenes from pellets production [paper III]

Most of the terpenes were emitted during the drying step. The materials dried in the rotary dryers both lost about 80% of the terpene content during drying. Sawdust dried in steam dryers lost 48 and 71% respectively of the initial terpene content.

During the production of pellets, 68-95% of the terpene content remaining in the dried sawdust was released. There was a correlation between the dried sawdust moisture content and terpene loss during pelleting: higher moisture content caused higher percentage losses. Since the moisture content of the dried sawdust varied considerably more than the moisture content of pellets, it is believed that high moisture sawdust have a longer residence time in the pelleting machine.

The amount of terpenes in wood dried to a moisture content suitable for production of pellets varied between 250 and 1110 mg/kg odw. The raw material with sawdust and cutter shavings from lumber dry boards did not differ from the other samples. The amount of terpenes in pellets was 14- 123 mg/kg odw, with five of the six samples clustering around 100 mg/kg odw1.

After the sawdust has been both dried and pelleted, almost all the volatile terpenes have been emitted. Consequently, sawdust with higher terpene content caused higher emissions during pelleting (figure 5.1).

terpenes 1,2 emitted during 1,0 pelleting (mg/kg) 0,8 0,6 A 0,4 C 0,2 D E 0,0 G 0,0 0,2 0,4 0,6 0,8 1,0 1,2 terpenes in dried sawdust (mg/kg) Figure 5.1. Terpenes emitted from dried sawdust during pelleting related to the terpenes left in sawdust after drying. This diagram was not included in paper III. Materials from producer G became available after the publication of paper III.

1 Values from producer G in mg/kg odw: before drying 2400, after drying 590, and pellets 90.

42 5.4. Biogenic emissions of terpenes [paper V]

Estimates of biogenic VOC emissions are important input for models of atmospheric chemistry and for carbon budgets (Geron et al., 1994), and for photochemical oxidant modelling (Simpson et al., 1999).

According to a frequently used model by Guenther et al., the emission flux is given by the equation

F = Dεγ where F is emission flux (µgC/m2h), D is foliar density (gdw/m2), ε is an ecosystem dependent emission factor (µgC/gdw h), and γ is an activity factor dependent on temperature (Guenther et al., 1995).

The review of factors affecting emissions [paper V] shows that light intensity and seasonal variation deserve to be included in models on biogenic terpene emissions. In addition, as tissue damage increases emissions, a base level of herbivory and insect predation should be assumed and included.

I also argue that the use of monthly estimates of biomass and temperature are insufficient for zones with a variable climate, like the boreal zone with strong seasonal variability of temperature and light as well as highly variable deciduous foliage density over the year.

To obtain predictive powers, the model should have sufficient time resolution to capture brief high concentrations that can be expected for example during bud break.

Most emission rate values are reported as normalised to 30°C using a temperature dependence factor of 0.09°C-1. I show that it is important to use a locally correct value of temperature dependence to recalculate reported values before they are used for modelling.

43 6. Conclusions

Whether emissions are natural or anthropogenic, terpenes become a problem when mixed with polluted air. Terpene emissions from dryers and pellets production are primarily a work environment issue. Natural emissions of monoterpenes from forests cause damage to vegetation, for example economically important trees and crops.

Terpene emissions from dryers can be measured, with good accuracy, despite problems with diffuse emissions and high moisture content of the drying medium.

To minimise VOC emissions from dryers, the sawdust moisture content should be kept above 10% and the drying medium temperature should not exceed 170°C. Low VOC emissions would improve the sawdust’s energy content and decrease air pollution around the drying facility.

An alternative approach is to increase emissions of VOC, by drying sawdust to less than 10% moisture content, using a high temperature drying medium. This would minimise emissions in subsequent processing, such as compressing to pellets. Since almost all of the monoterpenes remaining in sawdust after drying are released in the pelleting process, the question is not if emissions will occur but when and where. From a work environment perspective, the use of sawdust with low terpene content for pellets production is preferable.

The VOC emitted during drying would have to be collected or destroyed. The concentration of VOC in the drying medium was relatively constant in a spouted bed dryer in continuous operation at a wide range of sawdust moisture contents. Equipment for VOC separation or destruction would thus have even loads of VOC, which facilitate efficient processes.

Models of terpene emissions and atmospheric chemistry are necessary to assess the problems caused by natural terpene emissions. Models aiming at predicting terpene fluxes from natural sources should include several factors besides temperature. When identification of high concentrations are important, models must have sufficient time resolution to capture emission peaks. Furthermore, the temperature dependence varies sufficiently to motivate using specific values for the ecosystems examined.

44 7. Further research needs

The focus of this study is on volatile organic compounds, especially monoterpenes. For a more exhaustive knowledge of emissions of organic compounds during drying, the emissions of less volatile compounds could be further explored and the emitted sesquiterpenes and diterpenes identified and quantified.

One area for future research is to develop a prediction model for emission values based on known drying parameters. Such a model would benefit the industry by reducing the need for time-consuming VOC sampling. The construction of such a model for full-scale drying in a spouted bed in continuous operation necessitates measurements of VOC emissions during drying of other species of trees, as well as of bark and logging residues. Should the model also include other types of dryers, their emissions for different processed material should be studied.

The theoretical understanding of transport and emission processes at particle level could be expanded by modelling emissions of water and mono-, sesqui- and diterpenes. All these fractions have different vapour pressure, solubility and mass diffusion resistance.

Another area for future research is to integrate the drying technique with the energy systems of sawmills, or with municipal heating systems, so that the total environmental load caused by the system is optimised.

There are several interesting research issues in the field of pellets production techniques. One is if overdrying the sawdust compromises the quality properties of the produced pellets, e.g., their structural integrity. Sawdust with higher initial moisture content may have a longer residence time in the pellets press, and Davila (2002) found that high moisture content causes a higher temperature in the press.

Regarding natural terpene emissions from forests, some important areas of research are (1) the sensitivity of northern boreal species to herbivory and pest outbreaks - examination of the quantitative and qualitative differences between emissions from healthy trees and trees with various levels of damage, (2) are the observed latitudinal and longitudinal differences in emission factors due to climate, soil, genetically different strands, or other factors?, (3) seasonal variations - in particular monitoring of conifer emissions after October, and of deciduous trees’ emissions during their whole growth cycle.

45 8. Acknowledgements

Several persons have contributed to this work in various ways.

First of all, I wish to express my gratitude to my supervisor Professor Bengt Månsson for his support, encouragement, and constructive comments. I also appreciate our interesting discussions on various non-emission related subjects.

My assistant supervisor, Senior Lecturer Inge Svedung, deserves thanks for his inspiring ideas.

I wish to acknowledge Roger Renström, Jonas Berghel and Lars Pettersson, who constructed the spouted bed dryer used in my experiments. Lars has also provided assistance with the setting up of equipment for data acquisition, frequently with short notice.

Thanks are due to Gunnar Håkansson and Mikael Andersén at the Division for Chemistry, Karlstad University; to Gunnar for assistance with trouble-shooting of the GC-MS, and to Mikael for his unremitting willingness to lend laboratory ware.

My fellow PhD students and colleagues at the Department of Environmental and Energy Systems for making this such an enjoyable place to work.

Värmeforsk is gratefully acknowledged for financial support of the project Z9-828 “Emissions of volatile hydrocarbons during drying of sawdust”. Results from this project were published in Värmeforsk report 745, Utsläpp av lättflyktiga kolväten vid torkning av biobränslen (in Swedish with an English summary).

Svebio (the Swedish bioenergy association) deserves thanks for awarding me the Jan Häckners Stipendium (grant), which facilitated my travelling to distant conferences to make presentations of my research, gaining invaluable experiences in the process.

46 Appendix I. Chemical and physical data of monoterpenes

Monoterpenes are practically insoluble in water, see table AI 3 and AI 4. Terpenes with a higher boiling point are more soluble in water and less volatile, cf. table AI 1, AI 2, AI 3, AI 4 and AI 5.

Table AI.1. Monoterpenes’ boiling point, melting point and density. – indicates no available information. Monoterpene Boiling Point (°C) Melting Point (°C) Density (kg/l) α-pinene 156 -55 0.858 β-pinene 164 -61 0.865 myrcene 167 – 0.801 3-carene 167-168 – 0.844 p-cymene 176-178 – 0.860 limonene 177 -74 0.842 γ-terpinene 182 – 0.849 camphene 160 48-52 (crystals) 0.850

Table AI.2. Water Solubility of Monoterpenes (Li et al., 1998). Monoterpene Water Solubility at 23.5 °C Water Solubility at 6 °C (µmol terpene/liter H2O) (µmol terpene/liter H2O) α-pinene 18.3 +- 0.5 16.7 +- 0.7 limonene 41.0 +- 0.7 31.8 +- 1.0 γ-terpinene 63.7 +- 0.5 44.7 +- 0.5 terpinolene 69.6 +- 2.0 56.7 +- 0.7

Table AI.3. Partition coefficients of monoterpenes at 37 °C, mean and (standard deviation) of 20 samples (Falk-Filipsson, 1995).

Monoterpene Mwater/Mair Moil/Mair α-pinene 0.12 (0.36) 2900 (460) β-pinene 0.12 (0.27) 4300 (720) 3-carene 0.41 (0.58) 5000 (1200) limonene 1.8 (1.5) 5700 (1400)

Table AI.4. Vapour pressure of monoterpenes (Li et al., 1998). Monoterpene Vapour Pressure at 23.5 °C (Pa) Vapour Pressure at 6 °C (Pa) α-pinene 544 59.7 limonene 202 18.4 γ-terpinene 103 13.4 terpinolene 99.0 5.97

Table AI.5. Antoine constants for monoterpenes (Fengel and Wegener, 1984). Antoine equation: log P (mmHg) = A-B/(T+C); with T=temperature in °C Monoterpene Antoine Constant Antoine Constant Antoine Constant A B C α-pinene 6.9517 1511.961 215.42 β-pinene 6.9431 1539.348 213.21 3-carene 6.8477 1499.8 206.1 limonene 6.8485 1513.1 205.4 camphene 6.8462 1486.4 208.6

47 Appendix II. Symbols and abbreviations

CoA Co-Enzyme A FID Flame Ionisation Detector GC-MS Gas Chromatograph with Mass Spectrometer detector

MCend end moisture content of the dried wood odw oven dry weight ppm part per million (volume) T temperature T1 temperature of the drying medium entering the drying tower terpodw terpene emissions per oven dry weight Tmax maximum temperature of the drying medium VOC Volatile Organic Compounds

48 References

AFS, 2000. Hygieniska gränsvärden och åtgärder mot luftföroreningar. 2000:3, Arbetarskyddsstyrelsen Altshuller, A.P., 1983. Review: natural volatile organic substances and their effect on air quality in the United States. Atmospheric Environment, 17(11): 2131-2165. Atkinson, R., Aschmann, S. and Pitts, J., 1986. Rate constants for the gas-phase reactions of the OH-radical with a series of monoterpenes at 294°K. Int J Chem Kinet, 18: 287-299. Atkinson, R. and Carter, W., 1984. Kinetics and mechanisms of the gas-phase reactions of ozone with organic compounds under atmospheric conditions. Chem Rev, 84: 437-470. Axelsson, H., Boström, C.-Å., Cooper, D. and Svedberg, U., 1992. Measurements of terpene emissions from wood chip piles using FTIR. Nordic pulp and paper research journal, 3(7): 155-158. Back, E.L., 2002a. A pattern of parenchyma and canal resin chemistry in hardwoods and softwoods - 1. Review for softwoods. Nordic Pulp & Paper Research Journal, 17(2): 153-158. Back, E.L., 2002b. Pattern of parenchyma and canal resin composition in softwoods and hardwoods. Journal of Wood Science, 48(3): 167-170. Banerjee, S., 2001. Mechanisms of terpene release during sawdust and flake drying. Holzforschung, 55(4): 413-416. Banerjee, S., Hutten, M., Su, W., Otwell, L. and Newton, L., 1995. Release of Water and Volatile Organics from Wood Drying. Environmental Science & Technology, 29(4): 1135-1136. Banerjee, S. et al., 1998. Wet line extension reduces VOCs from softwood drying. Environmental Science & Technology, 32(9): 1303-1307. Bengtsson, P. and Sanati, M., 2004a. Evaluation of hydrocarbon emissions from heart- and sapwood of Scots pine using a laboratory-scale wood drier. Holzforschung, 58(6): 660-665. Bengtsson, P. and Sanati, M., 2004b. Measurement and mathematical modeling of the hydrocarbon emissions from wood drying., Proceedings of the 14th international drying symposium, Sao Paulo, Brazil, pp. 1352-1359. Berghel, J. and Renström, R., 2002. Basic design criteria and corresponding results performance of a pilot-scale fluidized superheated atmospheric condition steam dryer. Biomass & Bioenergy, 23(2): 103-112. Berghel, J. and Renström, R., 2004. Controllability of product moisture content when nonscreened sawdust is dried in a spouted bed. Drying Technology, 22(3): 507-519. Bridgwater, A. et al., 1995. The nature and control of solid, liquid and gaseous emissions from the thermochemical processing of biomass. Biomass and bioenergy, 9(325-341). Broege, K., Aehlig, K. and Scheithauer, M., 1996. Emissionen aus Schnittholztrocknern, Institut fur Holztechnologie Dresden Calogirou, A., Larsen, B.R. and Kotzias, D., 1999. Gas-phase terpene oxidation products: a review. Atmospheric Environment, 33(9): 1423-1439.

49 Conners, T.E. et al., 2001. Seasonal variation of southern pine terpenes. Forest Products Journal, 51(6): 89-94. Conners, T.E., Yan, H. and Banerjee, S., 2002. Mechanism of VOC release from high-temperature southern pine lumber drying. Wood and Fiber Science, 34(4): 666-669. Corchnoy, S.B. and Atkinson, R., 1990. Kinetics of the Gas-Phase Reactions of Oh and No3 Radicals with 2-Carene, 1,8-Cineole, Para-Cymene, and Terpinolene. Environmental Science & Technology, 24(10): 1497-1502. Cronin, E., 1979. Oil of turpentine – a disappearing allergen. Contact dermatitis, 5: 308-311. Dahlqvist, M. et al., 1992. Lung-Function and Precipitating Antibodies in Low Exposed Wood Trimmers in Sweden. American Journal of Industrial Medicine, 21(4): 549-559. Dahlqvist, M. et al., 1996. Acute effects of exposure to air contaminants in a sawmill on healthy volunteers. Occupational and Environmental Medicine, 53(9): 586-590. Dahlqvist, M. and Ulfvarson, U., 1994. Acute Effects on Forced Expiratory Volume in One Second and Longitudinal Change in Pulmonary-Function among Wood Trimmers. American Journal of Industrial Medicine, 25(4): 551-558. Danielsson, S. and Rasmuson, A., 2002. The influence of drying medium, temperature, and time on the release of monoterpenes during convective drying of wood chips. Drying Technology, 20(7): 1427-1444. Davila, E.A., 2002. Miljöanpassad energiproduktion och arbetsmiljö - tillverkning av träpellets. B1438, IVL Svenska Miljöinstitutet AB Edman, K. et al., 2003. Exposure assessment to alpha- and beta-pinene, Delta(3)- carene and wood dust in industrial production of wood pellets. Annals of Occupational Hygiene, 47(3): 219-226. Ek, M., Boström, C.-Å., Ljungqvist, P. and N-O, N., 2000. Rening och kemisk karakterisering av kondensat och torkgaser från torkning av biobränsle (In swedish with english summary). 683, Värmeforskrapport Englund, F. and Nussbaum, R.M., 2000. Monoterpenes in Scots pine and Norway spruce and their emission during kiln drying. Holzforschung, 54(5): 449- 456. Eriksson, K.A. et al., 1997. Terpene exposure and respiratory effects among workers in Swedish joinery shops. Scandinavian Journal of Work Environment & Health, 23(2): 114-120. Eriksson, K.A., Stjernberg, N.L., Levin, J.O., Hammarstrom, U. and Ledin, M.C., 1996. Terpene exposure and respiratory effects among sawmill workers. Scandinavian Journal of Work Environment & Health, 22(3): 182-190. Falk, A., Lof, A., Hagberg, M., Hjelm, E.W. and Wang, Z.P., 1991. Human Exposure to 3-Carene by Inhalation - Toxicokinetics, Effects on Pulmonary-Function and Occurrence of Irritative and Cns-Symptoms. Toxicology and Applied Pharmacology, 110(2): 198-205. Falk, A., Löf, A., Hagberg, M., Wigaeus-Hjelm, E. and Zhiping, W., 1990. Uptake, distribution and elimination of a-pinene in man after exposure by inhalation. Scandinavian journal of work environment & health, 16: 372- 378.

50 Falk-Filipsson, A., 1995. Toxicokinetics and acute effects of inhalation exposure to monoterpenes in man. Arbete och hälsa Pages. National institute of occupational health, Solna. Fengel, D. and Wegener, G., 1984. Wood: chemistry, ultrastructure, reactions Pages. De Gruyter, Berlin. Fyhr, C. and Rasmuson, A., 1996. Mathematical model of steam drying of wood chips and other hygroscopic porous media. Aiche Journal, 42(9): 2491- 2502. Geron, C.D., Guenther, A.B. and Pierce, T.E., 1994. An Improved Model for Estimating Emissions of Volatile Organic-Compounds from Forests in the Eastern United-States. Journal of Geophysical Research-Atmospheres, 99(D6): 12773-12791. Gershenzon, J., 1994. Metabolic Costs of Terpenoid Accumulation in Higher- Plants. Journal of Chemical Ecology, 20(6): 1281-1328. Gershenzon, J. and Croteau, R., 1991. Terpenoids. In: M.R. Berenbaum (Editor), Herbivores - their interactions with secondary plant metabolites. Academic press, San Diago, pp. 165-219. Gershenzon, J. and Croteau, R., 1992. Regulation of monoterpene biosynthesis in higher plants. In: H. Stafford (Editor), Biochemistry of the Mevalonic acid pathway to terpenoids. Plenum Press, New York, pp. 99-160. Goodwin, T. and Mercer, E., 1983. Introduction to plant biochemistry Pages. Pergamon press, Oxford. Granström, K., 2003. Emissions of monoterpenes and VOCs during drying of sawdust in a spouted bed. Forest Products Journal, 53(10): 48-55. Granström, K.M., 2001. Utsläpp av lättflyktiga kolväten vid torkning av biobränslen (eng: Emissions of Volatile Hydrocarbons (VOC) during Drying of Sawdust). 745, Värmeforskrapport Guenther, A. et al., 1995. A Global-Model of Natural Volatile Organic-Compound Emissions. Journal of Geophysical Research-Atmospheres, 100(D5): 8873- 8892. Halpin, D.M.G. et al., 1994a. Respiratory Symptoms, Immunological Responses, and Aeroallergen Concentrations at a Sawmill. Occupational and Environmental Medicine, 51(3): 165-172. Halpin, D.M.G., Graneek, B.J., Turnerwarwick, M. and Taylor, A.J.N., 1994b. Extrinsic Allergic Alveolitis and Asthma in a Sawmill Worker - Case- Report and Review of the Literature. Occupational and Environmental Medicine, 51(3): 160-164. Hatakeyama, S., Izumi, K., Fukuyama, T. and Akimoto, H., 1989. Reactions of Ozone with Alpha-Pinene and Beta-Pinene in Air - Yields of Gaseous and Particulate Products. Journal of Geophysical Research-Atmospheres, 94(D10): 13013-13024. Hedenstierna, G., Alexandersson, R., Wimander, K. and Rosén, G., 1983. Exposure to terpenes: effects on pulmonary function. International archives of occupational and environmental health, 51: 191-198. Hooker, C., Westberg, H. and Sheppard, J., 1985. Determination of carbon balances for smog chamber terpene oxidation experiments using 14C tracer technique. J Atmos Chem, 2: 307-320.

51 Ingram, L., Taylor, F. and Templeton, M., 1996. Volatile organic compound emissions from southern pine kilns, Drying pacific northwest species for quality control. Forest products society, Madison WI, pp. 41-45. Ingram, L.L., Shmulsky, R., Dalton, A.T., Taylor, F.W. and Templeton, M.C., 2000. The measurement of volatile organic emissions from drying southern pine lumber in a laboratory-scale kiln. Forest Products Journal, 50(4): 91- 94. Ingram, L.L., Taylor, F.W., Punsavon, V. and Templeton, M.C., 1995. Identification of volatile organic compounds emitted during drying of southern pine in pilot and laboratory experiments, Measuring and controlling VOC and particulate emissions from wood processing operations and wood based products. Forest Products Society, Madison WI, pp. 35-40. Janson, R.W., 1993. Monoterpene Emissions from Scots Pine and Norwegian Spruce. Journal of Geophysical Research-Atmospheres, 98(D2): 2839- 2850. Jirjis, R., 1995. Storage and drying of wood fuel. Biomass & Bioenergy, 9(1-5): 181-190. Jirjis, R. and Theander, O., 1990. The effect of seasonal storage on the chemical composition of forest residue chips. Scandinavian Journal of forest research, 58(3): 437-448. Johansson, A. and Rasmuson, A., 1998. The release of monoterpenes during convective drying of wood chips. Drying Technology, 16(7): 1395-1428. Johansson, I., 2002. Drying of biofuels at high dewpoints. Licentiate thesis Thesis, Number of Pages pp, Lund University, Department of chemical engineering 1. Karlsson, T., 2001. Terpene release during drying of wood flakes for particleboard manufacture. Licentiate thesis Thesis, Number of Pages pp, Lund university, Department of chemial engineering 1. Kasanen, J.P. et al., 1999. Evaluation of sensory irritation of Delta(3)-carene and turpentine, and acceptable levels of monoterpenes in occupational and indoor environment. Journal of Toxicology and Environmental Health-Part A, 57(2): 89-114. Kesselmeier, J. and Staudt, M., 1999. Biogenic volatile organic compounds (VOC): An overview on emission, physiology and ecology. Journal of Atmospheric Chemistry, 33(1): 23-88. Kotzias, D., Fytianos, K. and Geiss, F., 1990. Reaction of Monoterpenes with Ozone, Sulfur-Dioxide and Nitrogen-Dioxide Gas-Phase Oxidation of So2 and Formation of Sulfuric-Acid. Atmospheric Environment Part a-General Topics, 24(8): 2127-2132. Lavery, M.R. and Milota, M.R., 2000. VOC emissions from Douglas-fir: Comparing a commercial and a laboratory kiln. Forest Products Journal, 50(7-8): 39-47. Lavery, M.R. and Milota, M.R., 2001. Measurement of VOC emissions from ponderosa pine lumber using commercial and laboratory kilns. Drying Technology, 19(9): 2151-2173. Lerdau, M., Litvak, M. and Monson, R., 1994. Plant-Chemical Defense - Monoterpenes and the Growth-Differentiation Balance Hypothesis. Trends in Ecology & Evolution, 9(2): 58-61.

52 Lerdau, M., Matson, P., Fall, R. and Monson, R., 1995. Ecological Controls over Monoterpene Emissions from Douglas-Fir (Pseudotsuga-Menziesii). Ecology, 76(8): 2640-2647. Levin, J.-O., 1994. Biologisk kontroll vid yrkesmässig exponering för terpener. 24, Arbetslivsinstitutet Li, J., Perdue, E.M., Pavlostathis, S.G. and Araujo, R., 1998. Physicochemical properties of selected monoterpenes. Environment international, 24(3): 353- 358. Litvak, M.E., Madronich, S. and Monson, R.K., 1999. Herbivore-induced monoterpene emissions from coniferous forests: Potential impact on local tropospheric chemistry. Ecological Applications, 9(4): 1147-1159. Lundberg, P., 1987. Vetenskapligt underlag för hygieniska gränsvärden: terpentin och några monoterpener. Arbete och hälsa, 38: 128-137. Malmberg, P.O. et al., 1996. Increased bronchial responsiveness in workers sawing Scots pine. American Journal of Respiratory and Critical Care Medicine, 153(3): 948-952. Marutzky, R., 1979. Einfluss der lagerung von kiefernholz-Hackschnitzeln auf die emission bei der spantrocknung. 28, WKI-Kurzbericht Matura, M. et al., 2003. Patch testing with oxidized R-(+)-limonene and its hydroperoxide fraction. Contact Dermatitis, 49(1): 15-21. McDonald, A. and Wastney, S., 1995. Analysis of volatile emissions from kiln drying of radiata pine, Proceedings from 8th intern symposium on wood and pulping chemistry, Helsinki, pp. 431-436. McDonald, A.G., Dare, P.H., Gifford, J.S., Steward, D. and Riley, S., 2002. Assessment of air emissions from industrial kiln drying of Pinus radiata wood. Holz Als Roh-Und Werkstoff, 60(3): 181-190. Mujumdar, A.S. and Menon, A.S., 1995. Drying of solids: Principles classification and selection of dryers. In: A.S. Mujumdar (Editor), Handbook of industrial drying. Marcel Dekker, New York, pp. 1-39. Münter, M. et al., 1999. Teknisk och miljömässig analys av biobränsletorkar (In swedish with english summary). 662, Värmeforskrapport NCASI, 2002. A comparative study of VOC emissions from small-scale and full- scale lumber kilns drying Southern pine. 845, National Council for Air and Stream Improvement Nussbaum, R. and Englund, F., 1997. Utsläpp till luft av flyktiga organiska ämnen (VOC) från virkestorkar, förstudie. 9709085 P, TRÄTEK Petersson, G., 1997. Kemisk miljövetenskap Pages. Chalmers Reproservice, Göteborg. Raffa, K., 1991. "Phytochemical induction by herbivores". In: M.J. Raupp (Editor), Phytochemical induction by herbivores. Wiley, New York, pp. 245-276. Ruppe, K., 1929. Diseases and functional disturbances of the respiratory tract in workers of the woodworking industry. Z Gesamte Hyg, 19: 261-264. Schade, G.W. and Goldstein, A.H., 2003. Increase of monoterpene emissions from a pine plantation as a result of mechanical disturbances. Geophysical Research Letters, 30(7). Shmulsky, R., 2000. Influence of lumber dimension on VOC emissions from kiln- drying loblolly pine lumber. Forest Products Journal, 50(3): 63-66.

53 Sillman, S., 1999. The relation between ozone, NOx and hydrocarbons in urban and polluted rural environments. Atmospheric Environment, 33(12): 1821- 1845. Simpson, D. et al., 1999. Inventorying emissions from nature in Europe. Journal of Geophysical Research-Atmospheres, 104(D7): 8113-8152. Sjöström, E., 1981. Wood chemistry – Fundamentals and Applications Pages. Academic press, New York. Stangl, H., Kotzias, D. and Geiss, F., 1988. How Forest Trees Actively Promote Acid Deposition - the Role of Terpenes in the Dry Deposition of Ozone and Ozone Sulfur-Dioxide Mixtures. Naturwissenschaften, 75(1): 42-43. Staudt, M., Bertin, N., Frenzel, B. and Seufert, G., 2000. Seasonal variation in amount and composition of monoterpenes emitted by young Pinus pinea trees - Implications for emission modeling. Journal of Atmospheric Chemistry, 35(1): 77-99. Strömvall, A. and Petersson, G., 1991. Conifer monoterpenes emitted to air by logging operations. Scand J For Res, 6: 253-258. Strömvall, A.-M. and Petersson, G., 1999. Volatile terpenes emitted to air. In: L. Allen (Editor), Pitch control, wood resin and deresination. Tappi Press, Atlanta. Strömvall, A.M. and Petersson, G., 1990. Ambient Monoterpenes from Stone Groundwood Pulp Production. Holzforschung, 44(6): 449-452. Strömvall, A.M. and Petersson, G., 1992. Terpenes Emitted to Air from Tmp and Sulfite Pulp-Mills. Holzforschung, 46(2): 99-102. Strömvall, A.M. and Petersson, G., 1993a. Monoterpenes Emitted to Air from Industrial Barking of Scandinavian Conifers. Environmental Pollution, 79(3): 215-218. Strömvall, A.M. and Petersson, G., 1993b. Photooxidant-Forming Monoterpenes in Air Plumes from Kraft Pulp Industries. Environmental Pollution, 79(3): 219-223. Su, W., Yan, H. and Banerjee, S., 1999. Field-proven strategies for reducing volatile organic carbons from hardwood drying. Environmental Science & Technology, 33(7): 1056-1059. Svedberg, U. and Paulsson, S., 1995. Mätning av totalemissioner av terpener från sågverk och pappersbruk, Nordiska arbetsmiljömötet, Helsingfors, pp. 156- 7. Wu, J. and Milota, M.R., 1999. Effect of temperature and humidity on total hydrocarbon emissions from Douglas-fir lumber. Forest Products Journal, 49(6): 52-60. Yokouchi, Y. and Ambe, Y., 1985. Aerosols formed from the chemical reaction of monoterpenes and ozone. Atmospheric environment, 19: 1271-1276.

54 Emissions of volatile organic Karin Granström compounds from Emissions of volatile wood organic compounds from wood Division for Engineering Sciences, Physics and Mathematics Department of Environmental and Energy Systems

The central aim of this thesis is to support the efforts to counteract certain environ- mental problems caused by emissions of volatile organic compounds. The purpose of this work was (1) to develop a method to measure emissions from dryers, (2) to determine the effect of drying medium temperature and end moisture content of the processed material on emissions of monoterpenes and other hydrocar- Karin Granström bons, (3) to examine the emissions of monoterpenes during production of pellets, and (4) to examine the natural terpene emissions from forests with an eye to implications for modelling. The measurement method (1) resolves difficulties caused by diffuse emissions and high moisture content of the drying medium. The method as used here has an uncertainty of 13% using a 95% confidence interval. Emissions of volatile organic Emissions from a continuous spouted bed (2) drying sawdust at 140°C, 170°C or 200°C were analysed. When the sawdust end moisture content was reduced below 10%wb, emissions of terpenes and VOC per oven dry weight increased rapidly. Higher compounds from wood drying medium temperature also increased emissions. Examination of sawdust and wood pellets from different pellets producers (3) re- vealed that most of the terpene emissions happened during the drying step. Using sawdust with higher moisture content in the pellets press increased terpene emissions. Factors affecting terpene emissions from tree species in Sweden were reviewed (4). Implications for models of atmospheric chemistry and carbon budgets are discussed.

Karlstad University Studies Karlstad University Studies ISSN 1403-8099 2005:6 ISBN 91-85335-46-0