Understanding the organic chain : The framework of the interaction between the actors in organic chains in relation to ecological modernisation of food production

The sustainability of food production has increasingly attracted the attention of consumers, farmers, food and retailing companies, and politicians. One manifestation of such attention is the growing interest in organic foods. Organic agriculture has the potential to enhance the ecological modernisation of food production by implementing the organic method as a preventative innovation that simultaneously produces environmental and economic benefits. However, in addition to the challenges to organic farming, the small market share of organic products in many countries today and Finland in particular risks undermining the achievement of such benefits. The problems identified as hindrances to the increased consumption of organic food are the poor availability, limited variety and high prices of organic products, the complicated buying decisions and the difficulties in delivering the intangible value of organic foods. Small volumes and sporadic markets, high costs, lack of market information, as well as poor supply reliability are obstacles to increasing the volume of organic production and processing. These problems shift the focus from a single actor to the entire supply chain and require solutions that involve more interaction among the actors within the organic chain. As an entity, the organic food chain has received very little scholarly attention. Researchers have mainly approached the organic chain from the perspective of a single actor, or they have described its structure rather than the interaction between the actors. Consequently, interaction among the primary actors in organic chains, i.e. farmers, manufacturers, retailers and consumers, has largely gone unexamined. The purpose of this study is to shed light on the interaction of the primary actors within a whole organic chain in relation to the ecological modernisation of food production. This information is organised into a conceptual framework to help illuminate this complex field. This thesis integrates the theories and concepts of three approaches: food system studies, supply chain management and ecological modernisation. Through a case study, a conceptual system framework will be developed and applied to a real life-situation. The thesis is supported by research published in four articles. All examine the same organic chains through case studies, but each approaches the problem from a different, complementary perspective. The findings indicated that regardless of the coherent values emphasising responsibility, the organic chains were loosely integrated to operate as a system. The focus was on product flow, leaving other aspects of value creation largely aside. Communication with consumers was rare, and none of the actors had taken a leading role in enhancing the market for organic products. Such a situation presents unsuitable conditions for ecological modernisation of food production through organic food and calls for contributions from stakeholders other than those directly involved in the product chain. The findings inspired a revision of the original conceptual framework. The revised framework, the three-layer framework , distinguishes the different layers of interaction. By gradually enlarging the chain orientation the different but interrelated layers become visible. A framework is thus provided for further research and for understanding practical implications of the performance of organic food chains. The revised framework provides both an ideal model for organic chains in relation to ecological modernisation and demonstrates a situation consistent with the empirical evidence.

Temperature sensitivity of soil organic matter decomposition in boreal soils

The temperature sensitivity of decomposition of different soil organic matter (SOM) fractions was studied with laboratory incubations using 13C and 14C isotopes to differentiate between SOM of different age. The quality of SOM and the functionality and composition of microbial communities in soils formed under different climatic conditions were also studied. Transferring of organic layers from a colder to a warmer climate was used to assess how changing climate, litter input and soil biology will affect soil respiration and its temperature sensitivity. Together, these studies gave a consistent picture on how warming climate will affect the decomposition of different SOM fractions in Finnish forest soils: the most labile C was least temperature sensitive, indicating that it is utilized irrespective of temperature. The decomposition of intermediate C, with mean residence times from some years to decades, was found to be highly temperature sensitive. Even older, centennially cycling C was again less temperature sensitive, indicating that different stabilizing mechanisms were limiting its decomposition even at higher temperatures. Because the highly temperature sensitive, decadally cycling C, forms a major part of SOM stock in the organic layers of the studied forest soils, these results mean that these soils could lose more carbon during the coming years and decades than estimated earlier. SOM decomposition in boreal forest soils is likely to increase more in response to climate warming, compared to temperate or tropical soils, also because the Q10 is temperature dependent. In the northern soils the warming will occur at a lower temperature range, where Q10 is higher, and a similar increase in temperature causes a higher relative increase in respiration rates. The Q10 at low temperatures was found to be inversely related to SOM quality. At higher temperatures respiration was increasingly limited by low substrate availability.

Agronomic challenges for organic crop husbandry

With respect to resource management and environmental impact, organic farming offers rationales for agricultural sustainability. However, agronomic productivity is usually higher with conventional farming. This work aimed at investigating two factors of major importance for the agronomic productivity of organic crop husbandry, nitrogen (N) supply through symbiotic N fixation (SNF) and weed occurrence. Perennial red clover-grass leys and spring cereal crops subjected to regular agricultural practices were studied on 34 organic farms located in the southern and the north-western coastal regions of Finland. Herbage growth, clover content as a proportion of the ley and extent of SNF in perennial leys, and the occurrence of weed species and weed-crop competition in spring cereal stands were related to climate conditions, soil properties, and management measures. The herbage accumulated from the first and the second cut of one- and two-year-old leys averaged 7.5 t DM ha-1 (SD ± 1.7 t DM ha-1); the clover content averaged 43.9% (SD ± 18.8%). Along with the clover content, herbage production decreased with ley age. Radiation use efficiency (RUE) correlated positively with clover proportion but despite low clover contents, three-year-old leys were still productive with regard to RUE. SNF in the accumulated annual growth of one- and two-year-old leys averaged 247.5 kg N ha-1 yr-1 (SD ± 114.4 kg N ha-1 yr-1). It was supposed that if red clover-grass leys constituted 40% of the rotation, then the mean N supply by SNF would be able to sustain two or three succeeding cereal crops (green manure and forage ley, respectively), yielding 3.0 to 4.0 t grain ha-1. Being a function of clover biomass, the SNF increased from the first to the second cut and thereafter declined with ley age. Coefficients of variation of clover contents (and SNF) between and within fields were around 50%, which was about twice as high as those of herbage production. The lower were the clover contents, the higher were the within-field variations of clover as a proportion of the ley. Low clover contents in one-year-old leys and increasing variability with ley age suggested that red clover growth was limited by poor establishment and poor overwintering. The proportions of clover in leys were lower and their variability was higher in the northwest than in the south. Soil properties, primarily texture and structure, had a major impact on clover proportion and herbage production, which largely explained regional differences in ley growth. Within-field variability of soil properties can be amended through site-specific measures, including drainage, liming, and applications of organic manures and mineral fertilizers. Overwintering and the persistence of leys can be improved by the choice of winter-hardy varieties, careful establishment and the appropriate harvest regime. Mean grain yields of spring cereal crops amounted to 3.2 t ha-1 in the south and 3.6 t ha-1 in the northwest. At 570 and 565 m-2 for the south and northwest respectively, mean weed densities did not differ between the regions, whereas the respective mean weed biomass of 697 and 1594 kg dry weight ha-1, respectively did differ. Weed abundance varied remarkably between single fields. The number of weed species was higher in the south than in the northwest. For example, Fumaria officinalis and Lamium spp. were found only in the south. Frequencies and abundances of Lapsana communis, Myosotis arvensis, Polygonum aviculare, Tripleurospermum inodorum, and Vicia spp. were higher in the south, whereas those of Elymus repens, Persicaria spp. and Spergula arvensis were higher in the northwest. The number of years since conversion to organic farming, i.e. long-term management, was one of the variables that explained the abundance of single weed species. E. repens was the weed species whose biomass increased most with the duration of organic farming. Another significant variable was crop biomass, which was affected by short-term management. The presence of different weed species was related to the duration of organic farming and to low crop yield. This finding demonstrated that it was not the organic farming regime per se, which resulted in high weed infestation and low yielding crops, but failures in the understanding and the management of organic farming systems. Successful weed control relies on farm- and field-specific long- and short-term management approaches. The agronomic productivity of ley and spring cereal crops managed by full-time farmers with an interest in organic farming was on the same level as of the mean for conventional farming. Given the many options for further improvements of the agronomic performance of organic arable systems, organic farming offers foundations for the development of sustainable agriculture. The main threat to the sustainability of farming in Finland, both conventional and organic, is the spatial separation of crop production and animal husbandry by region, along with the simplification of associated crop rotations.

Characterization of Actinobacteria Degrading and Tolerating Organic Pollutants

Species of the genera Rhodococcus, Gordonia and Mycobacterium are known as degraders of recalcitrant pollutants. These bacteria are good survivors in harsh environments. Due to such properties these organisms are able to occupy a wide range of environmental niches. The members of these taxa have been suggested as tools for biotechnical applications such as bioremediation and biosynthesis. At the same time several of the species are known as opportunistic human pathogens. Therefore, the detailed characterization of any isolate that has potential for biotechnological applications is very important. This thesis deals with several corynebacterial strains originating from different polluted environments: soil, water-damaged indoor walls, and drinking water distribution systems. A polyphasic taxonomic approach was applied for characterization of the isolates. We found that the strains degrading monoaromatic compounds belonged to Rhodococcus opacus, a species that has not been associated with any health problem. The taxonomic position of strain B293, used for many years in degradation research under different names, was clarified. We assigned it to the species Gordonia polyisoprenivorans. This species is classified under European Biohazard grouping 1, meaning that it is not considered a health hazard for humans. However, there are reports of catheter-associated bacteraemia caused by G. polyisoprenivorans. Our results suggested that the ability of the organism to grow on phthalate esters, used as softeners in medical plastics, may be associated with the colonization of catheters and other devices. In this thesis Mycobacterium lentiflavum, a new emerging opportunistic human pathogen, was isolated from biofilms growing in public drinking water distribution systems. Our report on isolation of M. lentiflavum from water supplies is the second report on this species from drinking water systems, which may thus constitute a reservoir of M. lentiflavum. Automated riboprinting was evaluated for its applicability in rapidly identifying environmental mycobacteria. The technique was found useful in the characterization of several species of rapidly and slowly growing environmental mycobacteria. The second aspect of this thesis refers to characterization of the degradation and tolerance power of several R. opacus, M. murale and G. polyisoprenivorans strains. R. opacus GM-14 utilizes a wide range of aromatic substrates, including benzene, 15 different halobenzenes, 18 phenols and 7 benzoates. This study revealed the high tolerance of R. opacus strains toward toxic hydrophobic compounds. R. opacus GM-14 grew in mineral medium to which benzene or monochlorobenzene was added in amounts of 13 or 3 g l-1, respectively. R. opacus GM-29 utilized toluene and benzene for growth. Strain GM-29 grew in mineral medium with 7 g l-1 of liquid toluene or benzene as the sole carbon source, corresponding to aqueous concentrations of 470 and 650 mg l-1, respectively. Most organic solvents, such as toluene and benzene, due to their high level of hydrophobicity, pass through the bacterial membrane, causing its disintegration. In this thesis the mechanisms of adaptation of rhodococci to toxic hydrophobic compounds were investigated. The rhodococcal strains increased the level of saturation of their cellular fatty acids in response to challenge with phenol, chlorophenol, benzene, chlorobenzene or toluene. The results indicated that increase in the saturation level of cellular fatty acids, particularly that in tuberculostearic acid, is part of the adaptation mechanism of strains GM-14 and GM-29 to the presence of toxic hydrophobic compounds.

Microbial life and deposits in paper machine circuits

Väitöskirjani käsittele mikrobien ja erilaisten kemikaalien rooleja saostumien ja biofilmien muodostumisessa paperi- ja kartonkikoneilla. "Saostuma" tässä työssä tarkoittaa kiinteän aineen kertymää konepinnoille tai rajapinnoille konekierroissa, jotka on tarkoitettu massasulppujen, lietteiden, vesien tai ilman kuljetukseen. Saostumasta tulee "biofilmi" silloin kun sen oleellinen rakennekomponentti on mikrobisolut tai niiden tuotteet. Väitöstyöni työhypoteesina oli, että i. tietämys saostumien koostumuksesta, sekä ii. niiden rakenteesta, biologisista, fysikaalis-kemiallisista ja teknisistä ominaisuuksista ohjaavat tutkijaa löytämään ympäristöä säästäviä keinoja estää epätoivottujen saostumien muodostus tai purkaa jo muodostuneita saostumia. Selvittääkseni saostumien koostumista ja rakennetta käytin monia erilaisia analytiikan työkaluja, kuten elektronimikroskopiaa, konfokaali-laser mikroskopiaa (CLSM), energiadispersiivistä röntgenanalyysiä (EDX), pyrolyysi kaasukromatografiaa yhdistettynä massaspektrometriaan (Py-GCMS), joninvaihtokromatografiaa, kaasukromatografiaa ja mikrobiologisia analyysejä. Osallistuin aktiivisesti innovatiivisen, valon takaisinsirontaan perustuvan sensorin kehittämistyöhön, käytettäväksi biofilmin kasvun mittaukseen suoraan koneen vesikierroista ja säiliöistä. Työni osoitti, että monet paperinvalmistuksessa käytetyistä kemikaaleista reagoivat keskenään tuottaen orgaanisia tahmakerroksia konekiertojen teräspinnoille. Löysin myös kerrostumia, jotka valomikroskooppisessa tarkastelussa oli tulkittu mikrobeiksi, mutta jotka elektronimikroskopia paljasti alunasta syntyneiksi, alumiinihydroksidiksi joka saostui pH:ssa 6,8 kiertokuitua käyttävän koneen viiravesistä. Monet paperintekijät käyttävät vieläkin alunaa kiinnitysaineena vaikka prosessiolot ovat muuttuneet happamista neutraaleiksi. Sitä pidetään paperitekijän "aspiriinina", mutta väitöstutkimukseni osoitti sen riskit. Löysin myös orgaanisia saostumia, joiden alkuperä oli aineiden, kuten pihkan, saippuoituminen (kalsium saippuat) niin että muodostui tahmankasvua ylläpitävä alusta monilla paperi- ja kartonkikoneilla. Näin solumuodoiltaan Deinococcus geothermalista muistuttavia bakteereita kasvamassa lujasti teräskoepalojen pintaan kiinnittyneinä pesäkkeinä, kun koepaloja upotettiin paperikoneiden vesikiertoihin. Nämä deinokokkimaiset pesäkkeet voivat toimia jalustana, tarttumisalustana muiden mikrobien massoille, joka selittäisi miksi saostumat yleisesti sisältävät deinokokkeja pienenä, muttei koskaan pääasiallisena rakenneosana. Kun paperikoneiden käyttämien vesien (raakavedet, lämminvesi, biologisesti puhdistettu jätevesi) laatua tutkitaan, mittausmenetelmällä on suuri merkitys. Koepalan upotusmenetelmällä todettu biofilmikasvu ja viljelmenetelmällä mitattu bakteerisaastuneisuus korreloivat toisiinsa huonosti etenkin silloin kun likaantumisessa oli mukana rihmamaiseti kasvavia bakteereja. Huoli ympäristöstä on pakottanut paperi- ja kartonkikoneiden vesikiertojen sulkemiseen. Vesien kierrätys ja prosessivesien uudelleenkäyttö nostavat prosessilämpötilaa ja lisäävät koneella kiertävien kolloidisten ja liuenneiden aineiden määriä. Tutkin kiertovesien pitoisuuksia kolmessa eriasteisesti suljetussa tehtaassa, joiden päästöt olivat 0 m3, 0,5 m3 ja 4 m3 jätevettä tuotetonnia kohden, perustuen puhdistetun jäteveden uudelleen käyttöön. Nollapäästöisellä tehtaalla kiertovesiin kertyi paljon orgaanisesti sidottua hiiltä (> 10 g L-1), etenkin haihtuvina happoina (maito-, etikka-, propioni- ja voi-). Myös sulfaatteja, klorideja, natriumia ja kalsiumia kertyi paljon, > 1 g L-1 kutakin. Pääosa (>40%) kaikista bakteereista oli 16S rRNA geenisekvenssianalyysien tulosten perusteella sukua, joskin etäistä (< 96%) ainoastaan Enterococcus cecorum bakteerille. 4 m3 päästävältä tehtaalta löytyi lisäksi Bacillus thermoamylovorans ja Bacillus coagulans. Tehtaiden saostumat sisälsivät arkkeja suurina pitoisuuksina, ≥ 108 g-1, mutta tunnistukseen riittävää sekvenssisamanlaisuutta löytyi vain yhteen arkkisukuun, Methanothrix. Tutkimustulokset osoittivat että tehtaan vesikiertojen sulkeminen vähensi rajusti mikrobiston monimuotoisuutta, muttei estänyt liuenneen aineen ja kiintoaineen mineralisoitumista.

Nitrogen dynamics of organic farming in a crop rotation based on red clover (Trifolium pratense) leys

In agricultural systems which rely on organic sources of nitrogen (N), of which the primary source is biological N fixation (BNF), it is extremely important to use N as efficiently as possible with minimal losses to the environment. The amount of N through BNF should be maximised and the availability of the residual N after legumes should be synchronised to the subsequent plant needs in the crop rotation. Six field experiments in three locations in Finland were conducted in 1994-2006 to determine the productivity and amount of BNF in red clover-grass leys of different ages. The residual effects of the leys for subsequent cereals as well as the N leaching risk were studied by field measurements and by simulation using the CoupModel. N use efficiency (NUE) and N balances were also calculated. The yields of red clover-grass leys were highest in the two-year-old leys (6 700 kg ha-1) under study, but the differences between 2- and 3-year old leys were not high in most cases. BNF (90 kg ha-1 in harvested biomass) correlated strongly with red clover dry matter yield, as the proportion of red clover N derived from the atmosphere (> 85%) was high in our conditions of organically farmed field with low soil mineral N. A red clover content of over 40% in dry matter is targeted to avoid negative N-balances and to gain N for the subsequent crop. Surprisingly, the leys had no significant effect on the yields and N uptake of the two subsequent cereals (winter rye or spring wheat, followed by spring oats). On the other hand, yield and C:N of leys, as well as BNF-N and total-N incorporated into the soil influenced on subsequent cereal yields. NUE of cereals from incorporated ley crop residues was rather high, varying from 30% to 80% (mean 48%). The mineral N content of soil in the profile of 0-90 cm was low, mainly 15-30 kg ha-1. Simulation of N dynamics by CoupModel functioned satisfactorily and is considered a useful tool to estimate N flows in cropping systems relying on organic N sources. Understanding the long-term influence of cultivation history and soil properties on N dynamics remains to be a challenge to further research.

Organic contaminants - occurrence and biological effects in the Baltic Sea

The Baltic Sea was studied with respect to selected organic contaminants and their ecotoxicology. The research consisted of analyses of total hydrocarbons, polycyclic aromatic hydrocarbons, bile metabolites, hepatic ethoxyresorufin-O-deethylase (EROD) activity, polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). The contaminants were measured from various matrices, such as seawater, sediment and biota. The methods of analysis were evaluated and refined to comparability of the results. Polyaromatic hydrocarbons, originating from petroleum, are known to be among the most harmful substances to the marine environment. In Baltic subsurface water, seasonal dependence of the total hydrocarbon concentrations (THCs) was seen. Although concentrations of parent polycyclic aromatic hydrocarbons (PAHs) in sediment surface varied between 64 and 5161 ug kg-1 (dw), concentrations above 860 ug kg-1 (dw) were found in all the studied sub-basins of the Baltic Sea. Concentrations commonly considered to substantially increase the risk of liver disease and reproductive impairment in fish, as well as potential effects on growth (above 1000 ug kg-1 dw), were found in all the studied sub-basins of the Baltic Sea except Kattegat. Thus, considerable pollution in sediments was indicated. In bivalves, the sums of 12 PAHs varied on a wet weight basis between 44 and 298 ug kg-1 (ww). The predominant PAHs were high molecular weight and the PAH profiles of M. balthica differed from those found in sediment from the same area. The PAHs were both pyrolytic and petrogenic in origin, and a contribution from diesel engines was found, which indicates pollution of the Baltic Sea, most likely caused by the steadily increasing shipping in the area. The HPLC methods developed for hepatic EROD activity and bile metabolite measurements proved to be fast and suitable for the study of biological effects. A mixed function oxygenase enzyme system in Baltic Sea perch collected from the Gulf of Finland was induced slightly: EROD activity in perch varied from 0.30 14 pmol min-1 mg-1 protein. This range can be considered to be comparable to background values. Recent PAH exposure was also indicated by enhanced levels (213 and 1149 ug kg-1) of the bile metabolite 1-hydroxypyrene. No correlation was indicated between hepatic EROD activity and concentration of 1-hydroxypyrene in bile. PCBs and OCPs were observed in Baltic Sea sediment, bivalves and herring. Sums of seven CBs in surface sediment (0 5 cm) ranged from 0.04 to 6.2 ug kg-1 (dw) and sums of three DDTs from 0.13 to 5.0 ug kg-1 (dw). The highest levels of contaminants were found in the most eastern area of the Gulf of Finland where the highest total carbon and nitrogen content was found and where the lowest percentage proportion of p,p -DDT was found. The highest concentrations of CBs and the lowest concentration of DDTs were found in M. balthica from the Gulf of Finland. The highest levels of DDTs were found in M. balthica from the Hanö Bight, which is the outer part of the Bornholm Basin close to the Swedish mainland. In bivalves, the sums of seven CBs were 72 108 ug kg-1 (lw) and the sums of three DDTs were 66 139 ug kg-1 (lw). Results from temporal trend monitoring showed, that during the period 1985 2002, the concentrations of seven CBs in two-year-old female Baltic herring were clearly decreased, from 9 16 to 2 6 ug kg-1 (ww) in the northern Baltic Sea. At the same time, concentrations of three DDTs declined from 8 15 to 1 5 ug kg-1 (ww). The total concentration of the fat-soluble CBs and DDTs in Baltic herring muscle was shown to be age-dependent; the average concentrations in ten-year-old Baltic herring were three to five-fold higher than in two-year-old herring. In Baltic herring and bivalves, as well as in surface sediments, CB 138 and CB153 were predominant among CBs, whereas among DDTs p,p'-DDD predominated in sediment and p,p'-DDE in bivalves and Baltic herring muscle. Baltic Sea sediments are potential sources of contaminants that may become available for bioaccumulation. Based on ecotoxicological assessment criteria, cause for concern regarding CBs in sediments was indicated for the Gulf of Finland and the northern Baltic Proper, and for the northern Baltic Sea regarding CBs in Baltic herring more than two years old. Statistical classification of selected organic contaminants indicated high-level contamination for p,p'-DDT, p,p'-DDD, p,p'-DDE, total DDTs, HCB, CB118 and CB153 in muscle of Baltic herring in age groups two to ten years; in contrast, concentrations of a-HCH and g-HCH were found to be moderate. The concentrations of DDTs and CBs in bivalves is sufficient to cause biological effects, and demonstrates that long-term biological effects are still possible in the case of DDTs in the Hanö Bight.

Enzyme molecular choreography : studies on soluble inorganic pyrophosphatases

Inorganic pyrophosphatases (PPases, EC 3.6.1.1) hydrolyse pyrophosphate in a reaction that provides the thermodynamic 'push' for many reactions in the cell, including DNA and protein synthesis. Soluble PPases can be classified into two families that differ completely in both sequence and structure. While Family I PPases are found in all kingdoms, family II PPases occur only in certain prokaryotes. The enzyme from baker's yeast (Saccharomyces cerevisiae) is very well characterised both kinetically and structurally, but the exact mechanism has remained elusive. The enzyme uses divalent cations as cofactors; in vivo the metal is magnesium. Two metals are permanently bound to the enzyme, while two come with the substrate. The reaction cycle involves the activation of the nucleophilic oxygen and allows different pathways for product release. In this thesis I have solved the crystal structures of wild type yeast PPase and seven active site variants in the presence of the native cofactor magnesium. These structures explain the effects of the mutations and have allowed me to describe each intermediate along the catalytic pathway with a structure. Although establishing the ʻchoreographyʼ of the heavy atoms is an important step in understanding the mechanism, hydrogen atoms are crucial for the mechanism. The most unambiguous method to determine the positions of these hydrogen atoms is neutron crystallography. In order to determine the neutron structure of yeast PPase I perdeuterated the enzyme and grew large crystals of it. Since the crystals were not stable at ambient temperature, a cooling device was developed to allow neutron data collection. In order to investigate the structural changes during the reaction in real time by time-resolved crystallography a photolysable substrate precursor is needed. I synthesised a candidate molecule and characterised its photolysis kinetics, but unfortunately it is hydrolysed by both yeast and Thermotoga maritima PPases. The mechanism of Family II PPases is subtly different from Family I. The native metal cofactor is manganese instead of magnesium, but the metal activation is more complex because the metal ions that arrive with the substrate are magnesium different from those permanently bound to the enzyme. I determined the crystal structures of wild type Bacillus subtilis PPase with the inhibitor imidodiphosphate and an inactive H98Q variant with the substrate pyrophosphate. These structures revealed a new trimetal site that activates the nucleophile. I also determined that the metal ion sites were partially occupied by manganese and iron using anomalous X- ray scattering.

Properties of Ammonium Nitrate based fertilisers

The text is divided into three parts; Properties, Application and Safety of Ammonium Nitrate (AN) based fertilisers. In Properties, the structures and phase transitions of ammonium and potassium nitrate are reviewed. The consequences of phase transitions affect the proper use of fertilisers. Therefore the products must be stabilised against the volume changes and consequent loss of bulk density and hardness, formation of dust and finally caking of fertilisers. The effect of different stabilisers is discussed. Magnesium nitrate, ammonium sulphate and potassium nitrate are presented as a good compromise. In the Application part, the solid solutions in the systems (K+,NH4+)NO3- and (NH4+,K+)(Cl-,NO3-) are presented based on studies made with DSC and XRD. As there are clear limits for solute content in the solvent lattice, a number of disproportionation transitions exist in these process phases, e.g., N3 (solid solution isomorphous to NH4NO3-III) disproportionates to phases K3 (solid solution isomorphous to KNO3-III) and K2 (solid solution isomorphous to KNO3-II). In the crystallisation experiments, the formation of K3 depends upon temperature and the ratio K/(K+NH4). The formation of phases K3, N3, and K2 was modelled as a function of temperature and the mole ratios. In introducing chlorides, two distinct maxima for K3 were found. Confirmed with commercial potash samples, the variables affecting the reaction of potassium chloride with AN are the particle size, time, temperature, moisture content and amount of organic coating. The phase diagrams obtained by crystallisation studies were compared with a number of commercial fertilisers and, with regard to phase composition, the temperature and moisture content are critical when the formation and stability of solid solutions are considered. The temperature where the AN-based fertiliser is solidified affects the amount of compounds crystallised at that point. In addition, the temperature where the final moisture is evaporated affects the amount and type of solid solution formed at this temperature. The amount of remaining moisture affects the stability of the K3 phase. The K3 phase is dissolved by the moisture and recrystallised into the quantities of K3, which is stable at the temperature where the sample is kept. The remaining moisture should not be free; it should be bound as water in the final product. The temperatures during storage also affect the quantity of K3 phase. As presented in the figures, K3 phase is not stable at temperatu¬res below 30 °C. If the temperature is about 40 °C, the K3 phase can be formed due to the remaining moisture. In the Safety part, self-sustaining decomposition (SSD), oxidising and energetic properties of fertilisers are discussed. Based on the consequence analysis of SSD, early detection of decomposition in warehouses and proper temperature control in the manufacturing process is important. SSD and oxidising properties were found in compositions where K3 exists. It is assumed that potassium nitrate forms a solid matrix in which AN can decompose. The oxidising properties can be affected by the form of the product. Granular products are inherently less oxidising. Finally energetic properties are reviewed. The composition of the fertiliser has an importance based on theoretical calculations supported by experimental studies. Materials such as carbonates and sulphates act as diluents. An excess of ammonium ions acts as a fuel although this is debatable. Based on the experimental work, the physical properties have a major importance over the composition. A high bulk density is of key importance for detonation resistance.

Ionic Liquids and Microwaves in Promotion of Organic Synthesis : Friedel-Crafts reaction, deuterolabelling and O-Demethylation

The use of ionic liquids in chemical research has gained considerable interest and activity in recent years. Due to their unique and varied physicochemical properties, in comparison to molecular solvents, the potential applications for ionic liquids are enormous. The use of microwave irradiation, as a powerful dielectric heating technique, in synthetic organic chemistry has been known since 1986. Since then, it has gained significant recognition for its research and application in both academia and industry. The use of either ionic liquids or microwave irradiation in synthetic organic chemistry has been known to afford improved, alternative or complimentary selectivities, in comparison to traditional processes. In this study, the use of ionic liquids as solvents, co-solvents and catalytic media was explored in Friedel-Crafts, deuterolabelling and O-demethylation reactions. Alternative methods for the production of a variety of aromatic ketones using the Friedel-Crafts acylation methodology were investigated using ionic liquid catalyst or ionic liquid acidic additive systems. The disclosed methods, i.e. metal bistriflamides and chloroindate ionic liquids systems, possessed good catalytic activity in the synthesis of typical benzophenones. These catalytic systems were also recyclable. Microwave irradiation was found to be useful in the synthesis of various polyhydroxydeoxybenzoins and arylpropanones as synthetic precursors to naturally occurring or potentially bioactive compounds. Under optimized condition, the reaction occurred in only four minutes using systems such as [bmim][NTf2]/HNTf2 and [bmim][BF4]/BF3·OEt2. Naturally occurring polyphenols, such as isoflavones, can possess various types of biological or pharmacological activity. In particular, some are noted for their beneficial effects on human health. Isotopically labelled analogues of polyphenols are valuable as analytical standards in the quantification of these compounds from biological matrices. A new strategy for deuterolabelling of polyphenols was developed using ionic liquids as co-solvents and 35% DCl/D2O, as a cheap deuterium source, under microwave irradiation. Under these conditions, perdeuterated compounds were achieved in short reaction times, in high isotopic purity and in excellent yields. An O-demethylation reaction was developed, using an ionic liquid reaction medium with BBr3 for the deprotection of a variety methyl protected polyphenolic compounds, such as isoflavons and lignans. This deprotection procedure was found to be very practical as the reaction occurred under mild reaction conditions and in short reaction times. The isolation and purification steps were particularly straightforward and high yielding, in comparison to traditional methods.