Resin and fatty acids (RFA) are predominantly components of coniferous trees having the natural function of protecting against microbial damage. These compounds are released from wood during the pulping process and a fraction reaches the wastewater treatment system. RFA are acutely toxic to aquatic organisms at concentrations on the order of parts per million, and their presence has been linked to toxicity outbreaks in receiving waters following process upsets. The chronic toxicity of resin and fatty acids in complex effluent matrices is poorly understood. Furthermore, the role of hydrophobic, pulp-derived solids as a removal pathway from wastewater streams has not been comprehensively studied. The objectives of this dissertation have been to quantify the relationship between resin and fatty acid concentration and chronic toxicity and to determine the role of partitioning in the removal of these compounds from pulp mill wastewater streams. Field and laboratory studies were conducted to measure toxicity using the Microtox™ whole effluent toxicity and Ceriodaphnia dubia 7-day, survival and reproduction bioassays. One resin acid in particular, dehydroabietic acid, was found to account for a significant fraction of final effluent chronic toxicity. Dissolved and sorbed RFA concentrations were quantified by solvent extraction, methyl ester derivatization, and GC-FID analysis. Partitioning to suspended solids was found to be a major removal pathway for the RFA from the effluent treatment system. A kinetic model for flotation was applied and compared to experimental data. Flotation was found to be effective at selectively removing RFA bound to pulp-derived solids from pulp mill and bleach plant sewers at moderate to high pH.

The aims of the work this thesis is based upon were to develop convenient analytical procedures for determining resin acids in biological and environmental matrices, and apply them to enhance understanding of the occurrence, exposure to and uptake by exposed individuals of resin acids. Particular focus has been on the workplace environment of the Swedish wood pellets industry. Sample extraction procedures and high-performance liquid chromatography/electrospray ionisation-mass spectrometry (HPLC/ESI-MS) methodologies were developed for measuring resin acids in dust, skin and urine samples. Chromatographic separation of abietic (AA) and pimaric acid was achieved by using a polar-embedded C12 stationary phase. The HPLC/ESI-MS method avoids undesirable oxidation of AA, which was found to occur during the derivatisation step in the standard MDHS 83/2 gas chromatography/flame ionisation detection (GC/FID) methodology, leading to false observations of both AA and the oxidation product 7-oxodehydroabietic acid (7-OXO). Personal exposures to resin acids in the Swedish wood pellet production industry were found to be lower, on average, than the British Occupational Exposure Limit for rosin (50 µg/m3). The oxidised resin acid 7-OXO, was detected in both dust and skin samples indicating the presence of allergenic resin acids. A correlation between air and post-shift urinary concentrations of dehydroabietic acid (DHAA), and a trend towards an increase in urinary 7-OXO during work shifts, were also observed. Whether the increase in 7-OXO was due to direct uptake or metabolism of other resin acids cannot be concluded from the results. An efficient HPLC/UV methodology with diode-array detection was developed for screening commercial products for rosin that could be used in laboratories lacking mass spectrometers. Very high concentrations of free resin acids were detected in depilatory wax strips using the method. / At the time of doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Submitted.

Wood pellets have become a solid biomass fuel of choice because they are a standardized product with known quality properties. However, the self-heating and off-gassing tendencies during storage of wood pellets threatens the consistency of the pellets’ quality properties. The aim of this thesis was to increase the body of knowledge towards understanding of the off-gassing of wood pellets. The effects of total wood extractive content and types of extractives in the raw material on off-gassing of wood pellets were investigated through two separate studies. In the first study, the pellets were produced from fresh and pre-treated Scots pine sawdust. The pre-treatments involved storing, extraction and adding additive oils. The second study used synthetic pure cellulose that was pre-treated by adding different additive oils. The pellets were subjected to off-gassing tests under controlled conditions. The results from the first study showed that the total amount of extractives in the raw material has little effect on off-gassing. While gas emissions were reduced for stored and acetone extracted pine pellets, the coefficients of determination (R2) from the linear correlation analysis between off-gassing and the total extractive content of the raw materials were below 0.5 for all the three off-gasses indicating no correlation. The results of cellulose pellets with added additive oils in the second study showed that the off-gassing is highly dependent on the type of extractives in the raw material. The highest mean concentrations of the carbon oxides and methane were recorded from cellulose pellets with added linseed oil. Pellets with added linseed oil had higher off-gas emissions due to the high content of unsaturated fatty acids of 73.9% linolenic and 7.6% linoleic. Based on these results, it was concluded that one of the main causes of off-gassing during storage of wood pellets is the α-oxidation of unsaturated fatty acids. The other notable effect was that methane formation is dependent on anaerobic conditions, whereas formation of carbon oxides can occur both under aerobic and anaerobic conditions. / Wood pellets have over the years become a solid biomass fuel of choice for heat and power generation because they are a standardized product with known quality properties. However, the self-heating and off-gassing tendencies of wood pellets threatens the consistency of the quality properties. Self-heating and off-gassing can cause disintegration of the pellets resulting in dry matter losses and reduction in quality properties. Additionally, self-heating may lead to fires while off-gassing of toxic gasses such as carbon monoxide is a human health and environmental hazard. The aim of this thesis was to increase the body of knowledge towards the understanding of off-gassing of wood pellets. The results showed that total amount of extractives in the raw material has little effect on off-gassing. One of the main causes of off-gassing of carbon oxides by wood pellets is the α-oxidation of unsaturated fatty acids and other triglyceride oils that are chemically unstable. The other notable effect was that methane formation is dependent on anaerobic conditions, whereas formation of carbon oxides can occur both under aerobic and anaerobic conditions. / <p>This study was part of the project on secure and well-characterised raw materials and products through innovative adaption of pellets manufacturing processes (SVINPELS, project no 47997–1). This was a collaborative research project between Karlstad University and the Swedish University of Agricultural Sciences, SLU and was funded by the Swedish Energy Agency.</p>

Abstract The SOM in boreal forests contains non-living heterogeneous components resulting from microbial and chemical transformations of organic debris from plant litter. The major components in the plant biomass all decompose at different rates and therefore, contribute variably to the stable storages of soil C. The aims of the current thesis were 1) to explore how climate, soil fertility and initial litter quality affect the decomposition rate of litter, 2) to study how the different carbon fractions found in the plant litter relate to the quality and quantity of SOM in forest soils, 3) to determine whether the recalcitrant fraction of litter is derived from lignin and other polyphenols or from lipophilic compounds and carbohydrates, and 4) to determine whether the litter originating from different plant growth forms affects SOM formation in a similar way. The study was conducted in six north boreal and six south boreal study sites, half of which were mesic and half were sub-xeric. The overall initial litter quality and decomposition rate of carbon fractions did not differ between the two fertility levels and climate regimes. Litter with high initial water-soluble extractives (WSE) and nitrogen (N) decomposed at a faster rate than litter with lower initial WSE and N concentration irrespective of the soil fertility or climate conditions. Although decomposition rate varies among litter types, decomposition rate cannot explain differences in SOM quality or quantity between the northern and southern boreal forests. The organic matter accumulation and relative proportion of acid-insoluble residue (AIR) in SOM was higher in south boreal sites both in sub-xeric and mesic sites. Detailed characterization of the AIR fraction using pyrolysis-GC demonstrated that in the litter layer the concentration of AIR contains lignin and other insoluble polyphenols, but in the F and H layers, lignin-derived and chemically modified polyphenolics and decomposition products of resin acids. Although the concentration of the AIR fraction varies among litter types, its composition varied very little among the litter types, and between a sub-xeric and a mesic site. The results of this study suggest that the differences in plant community structure and quantitative differences in the litter input by various growth forms has more impact on OM accumulation than decomposition conditions in coniferous soils. / Tiivistelmä Metsämaan orgaaninen aines koostuu eriasteisesti hajonneesta karikkeesta sekä pitkälle maatuneesta, hajottajien muokkaamasta humuksesta. Tutkimuksessa selvitettiin 1) kuinka ilmasto, maaperän ravinteisuus ja karikkeen kemialliset ominaisuudet vaikuttavat karikkeen hajoamisnopeuteen, 2) kuinka kasvien sisältämät erilaiset hiilifraktiot vaikuttavat maaperän orgaanisen aineen laatuun ja määrään, 3) millaiset hiiliyhdisteet muodostavat vaikeimmin hajoavan hiilifraktion karikkeessa ja pidemmälle maatuneessa orgaanisessa aineessa ja 4) onko erilaisten kasvien vaikutus orgaanisen aineksen muodostumiseen samanlainen kuusikoissa ja männiköissä pohjois- ja eteläboreaalisella havumetsävyöhykkeellä. Tutkimuksessa havaittiin, että karikkeen maatumisnopeudessa ei ollut eroja pohjois- ja eteläboreaalisella kasvuvyöhykkeellä eikä kuusikoiden ja männiköiden väillä. Karike, joka sisälsi runsaasti vesiliukoisia yhdisteitä ja typpeä maatui nopeammin kuin vähän vesiliukoisia yhdisteitä tai typpeä sisältävä karike. Karikkeen maatumisnopeus ei kuitenkaan kyennyt selittämään eroja pidemmälle maatuneen orgaanisen aineksen määrässä ja laadussa pohjois- ja eteläboreaalisella kasvuvyöhykkeellä. Orgaanisen aineksen määrä oli suurempi eteläboreaalisella kasvuvyöhykkeellä verrattuna pohjoisboreaaliseen. Lisäksi vaikeasti hajoavia hiiliyhdisteitä (AIR-fraktio) kertyi eteläboreaaliseen metsämaahan enemmän kuin pohjoiseen. Karikekerroksessa ligniini ja polyfenolit muodostivat suuren osan AIR-fraktiosta. Maatumisen edetessä AIR-fraktion muodostavat lähinnä ligniinin hajoamisesta peräisin olevat ja muut modifioituneet polyfenolit sekä pihkahappojen hajoamistuotteet. Vaikka AIR-fraktion konsentraatio vaihteli kariketyypeittäin, sen kemiallinen koostumus oli hyvin samanlainen karikelajista riippumatta. Tutkimuksen perusteella vallitseva kasvillisuus ja sen tuottaman karikkeen määrä ja laatu vaikuttavat enemmän metsämaahan kertyvän orgaanisen aineen määrään kuin maatumisolosuhteet.

This work focuses on wood extractives in effluents from the CTMP plant at Skoghall Mill. Pulp and paper industry effluents contain mostly natural compounds which are part of the trees. They are toxic to aquatic life but harmless in nature, as they are present in low concentrations. Processing tons of wood, such as in a pulp mill, strongly increases the concentrations of the toxic compounds (Ali, M. and Sreekrishnan, T., 2001) which have to be treated before transferring to the aquatic environment.Extractives can be found in different forms, as micelles soluble in water, unprocessed in fibers or absorbed on the surface of fibers. It is important to know in which forms extractives are mostly present in the effluent, so that they can be treated more efficiently. It is desired to have extractives absorbed on the fibers and fibrils present in the waste water, so they can be separated from the water and treated separately, e.g. burned for energy recovery. Dissolved extractives complicate the oxygen transfer in an aerated biological treatment step with their surface active properties (Sandberg, 2012).The aim of this study is quantification of extractives on the fibers suspended in the waste water and extractives dissolved in the water. The distribution between the two forms is an important input when designing future effluent treatment. Wood extractives itself are a wide group with different compounds. This work focuses on the main groups present in waste water: resin acids, free and esterified fatty acids and, free and esterified sterols. These groups are analyzed in different process waters and waste water before the waste water treatment plant. The measured concentrations of extractives were as expected, higher in process and effluent waters, lower in white water. Most of the extract was dissolved in the water and unfortunately fiber samples contained very low concentration from the total extract in the samples.