Measurements of Volatile Organic Compounds - from Biogenic Emissions to Concentrations in Ambient Air

Volatile organic compounds (VOCs) affect atmospheric chemistry and thereafter also participate in the climate change in many ways. The long-lived greenhouse gases and tropospheric ozone are the most important radiative forcing components warming the climate, while aerosols are the most important cooling component. VOCs can have warming effects on the climate: they participate in tropospheric ozone formation and compete for oxidants with the greenhouse gases thus, for example, lengthening the atmospheric lifetime of methane. Some VOCs, on the other hand, cool the atmosphere by taking part in the formation of aerosol particles. Some VOCs, in addition, have direct health effects, such as carcinogenic benzene. VOCs are emitted into the atmosphere in various processes. Primary emissions of VOC include biogenic emissions from vegetation, biomass burning and human activities. VOCs are also produced in secondary emissions from the reactions of other organic compounds. Globally, forests are the largest source of VOC entering the atmosphere. This thesis focuses on the measurement results of emissions and concentrations of VOCs in one of the largest vegetation zones in the world, the boreal zone. An automated sampling system was designed and built for continuous VOC concentration and emission measurements with a proton transfer reaction - mass spectrometer (PTR-MS). The system measured one hour at a time in three-hourly cycles: 1) ambient volume mixing-ratios of VOCs in the Scots-pine-dominated boreal forest, 2) VOC fluxes above the canopy, and 3) VOC emissions from Scots pine shoots. In addition to the online PTR-MS measurements, we determined the composition and seasonality of the VOC emissions from a Siberian larch with adsorbent samples and GC-MS analysis. The VOC emissions from Siberian larch were reported for the fist time in the literature. The VOC emissions were 90% monoterpenes (mainly sabinene) and the rest sesquiterpenes (mainly a-farnesene). The normalized monoterpene emission potentials were highest in late summer, rising again in late autumn. The normalized sesquiterpene emission potentials were also highest in late summer, but decreased towards the autumn. The emissions of mono- and sesquiterpenes from the deciduous Siberian larch, as well as the emissions of monoterpenes measured from the evergreen Scots pine, were well described by the temperature-dependent algorithm. In the Scots-pine-dominated forest, canopy-scale emissions of monoterpenes and oxygenated VOCs (OVOCs) were of the same magnitude. Methanol and acetone were the most abundant OVOCs emitted from the forest and also in the ambient air. Annually, methanol and mixing ratios were of the order of 1 ppbv. The monoterpene and sum of isoprene 2-methyl-3-buten-2-ol (MBO) volume mixing-ratios were an order of magnitude lower. The majority of the monoterpene and methanol emissions from the Scots-pinedominated forest were explained by emissions from Scots pine shoots. The VOCs were divided into three classes based on the dynamics of the summer-time concentrations: 1) reactive compounds with local biological, anthropogenic or chemical sources (methanol, acetone, butanol and hexanal), 2) compounds whose emissions are only temperaturedependent (monoterpenes), 3) long-lived compounds (benzene, acetaldehyde). Biogenic VOC (methanol, acetone, isoprene MBO and monoterpene) volume mixing-ratios had clear diurnal patterns during summer. The ambient mixing ratios of other VOCs did not show this behaviour. During winter we did not observe systematical diurnal cycles for any of the VOCs. Different sources, removal processes and turbulent mixing explained the dynamics of the measured mixing-ratios qualitatively. However, quantitative understanding will require longterm emission measurements of the OVOCs and the use of comprehensive chemistry models. Keywords: Hydrocarbons, VOC, fluxes, volume mixing-ratio, boreal forest

Micro-treatment options for components of organic fraction of MSW in residential areas

There is a growing interest in management of MSW through micro-treatment of organic fraction of municipal solid wastes (OFMSW) in many cities of India. The OFMSW fraction is high (> 80%) in many pockets within South Indian cities like Bangalore, Chikkamagalur, etc. and is largely represented by vegetable, fruit, packing and garden wastes. Among these, the last three have shown problems for easy decomposition. Fruit wastes are characterized by a large pectin supported fraction that decomposes quickly to organic acids (becomes pulpy) that eventually slow down anaerobic and aerobic decomposition processes. Paper fraction (newsprint and photocopying paper) as well as paddy straw (packing), bagasse (from cane juice stalls) and tree leaf litter (typical garden waste and street sweepings) are found in reasonably large proportions in MSW. These decompose slowly due to poor nutrients or physical state. We have examined the suitability of these substrates for micro-composting in plastic bins by tracking decomposition pattern and physical changes. It was found that fruit wastes decompose rapidly to produce organic acids and large leachate fraction such that it may need to be mixed with leachate absorbing materials (dry wastes) for good composting. Leaf litter, paddy straw and bagasse decompose to the tune of 90, 68 and 60% VS and are suitable for composting micro-treatment. Paper fractions even when augmented with 10% leaf compost failed to show appreciable decomposition in 50 days. All these feedstocks were found to have good biological methane potential (BMP) and showed promise for conversion to biogas under a mixed feed operation. Suitability of this approach was verified by operating a plug-flow type anaerobic digester where only leaf litter gathered nearby (as street sweepings) was used as feedstock. Here only a third of the BMP was realized at this scale (0.18 m(3) biogas/kg VS 0.55 m(3)/kg in BMP). We conclude that anaerobic digestion in plug-flow like digesters appear a more suitable micro-treatment option (2-10 kg VS/day) because in addition to compost it also produces biogas for domestic use nearby.

Food waste, power, and corporate social responsibility in the Australian food supply chain

By examining corporate social responsibility (CSR) and power within the context of the food supply chain, this paper illustrates how food retailers claim to address food waste while simultaneously setting standards that result in the large-scale rejection of edible food on cosmetic grounds. Specifically, this paper considers the powerful role of food retailers and how they may be considered to be legitimately engaging in socially responsible behaviors to lower food waste, yet implement practices that ultimately contribute to higher levels of food waste elsewhere in the supply chain. Through interviews with key actors in the Australian fresh fruit and vegetable supply chain, we highlight the existence of a legitimacy gap in corporate social responsibility whereby undesirable behaviors are pushed elsewhere in the supply chain. It is argued that the structural power held by Australia’s retail duopoly means that supermarkets are able to claim virtuous and responsible behaviors, despite counter claims from within the fresh food industry that the food supermarkets’ private quality standards mean that fresh food is wasted. We argue that the supermarkets claim CSR kudos for reducing food waste at the expense of other supply chain actors who bear both the economic cost and the moral burden of waste, and that this is a consequence of supermarkets’ remarkable market power in Australia.

Regulating Food Consumption : Studies of change and variation in Europe

The role of people as buyers and eaters of food has changed significantly. From being protected by a paternalistic welfare state, people appear to be accorded more freedom and responsibility as individuals, where attention is redirected from the state towards market relations. Many have asserted that these changes are accompanied by fragmentation, individualisation, and privatisation, leading to individual uncertainty and lack of confidence. But empirical observations do not always confirm this, distrust is not necessarily growing and while responsibilities may change, the state still plays an active role. This dissertation explores changing relationships between states and markets, on the one hand, and ordinary people in their capacities as consumers and citizens, on the other. Do we see the emergence of new forms of regulation of food consumption? If so, what is the scope and what are the characteristics? Theories of regulation addressing questions about individualisation and self-governance are combined with a conceptualisation of consumption as processes of institutionalisation, involving daily routines, the division of labour between production and consumption, and the institutional field in which consumption is embedded. The analyses focus on the involvement of the state, food producers and scientific, first of all nutritional, expertise in regulating consumption, and on popular responses. Two periods come out as important, first when the ideas of “designing the good life” emerged, giving the state a very particular role in regulating food consumption, and, second, when this “designing” is replaced by ideas of choice and individual responsibility. One might say that “consumer choice” has become a mode of regulation. I use mainly historical studies from Norway to analyse the shifting role of the state in regulating food consumption, complemented with population surveys from six European countries to study how modernisation processes are associated with trust. The studies find that changing regulation is not only a question of societal or state vs individual responsibilities. Degrees of organisation and formalisation are important as well. While increasing organisation may represent discipline and abuses of power (including exploitation of consumer loyalty), organisation can also, to the consumer, provide higher predictability, systems to deal with malfeasance, and efficiency which may provide conditions for acting. The welfare state and the neo-liberal state have very different types of solutions. The welfare state solution is based on (national) egalitarianism, paternalism and discipline (of the market as well as households). Such solutions are still prominent in Norway. Individualisation and self-regulation may represent a regulatory response not only to a declining legitimacy of this kind of interventionism, but also increasing organisational complexity. This is reflected in large-scale re-regulation of markets as well as in relationships with households and consumers. Individualisation of responsibility is to the consumer not a matter of the number of choices that are presented on the shelves, but how choice as a form of consumer based involvement is institutionalised. It is recognition of people as “end-consumers”, as social actors, with systems of empowerment politically as well as via the provisioning system. ‘Consumer choice’ as a regulatory strategy includes not only communicative efforts to make people into “choosing consumers”, but also the provision of institutions which recognise consumer interests and agency. When this is lacking we find distrust as representing powerlessness. Individual responsibility-taking represents agency and is not always a matter of loyal support to shared goals, but involves protest and creativity. More informal (‘communitarian’) innovations may be an indication of that, where self-realisation is intimately combined with responsibility for social problems. But as solutions to counteract existing imbalances of power in the food market the impacts of such initiatives are probably more as part of consumer mobilisation and politicisation than as alternative provisioning.

Trust and Safe Choices: Coping with health-related risks in food consumption in St. Petersburg

This dissertation considers the problem of trust in the context of food consumption. The research perspectives refer to institutional conditions for consumer trust, personal practices of food consumption, and strategies consumers employ for controlling the safety of their food. The main concern of the study is to investigate consumer trust as an adequate response to food risks, i.e. a strategy helping the consumer to make safe choices in an uncertain food situation. "Risky" perspective serves as a frame of reference for understanding and explaining trust relations. The original aim of the study was to reveal the meanings applied to the concepts of trust, safety and risks in the perspective of market choices, the assessments of food risks and the ways of handling them. Supplementary research tasks presumed descriptions of institutional conditions for consumer trust, including descriptions of the food market, and the presentation of food consumption patterns in St. Petersburg. The main empirical material is based on qualitative interviews with consumers and interviews and group discussions with professional experts (market actors, representatives of inspection bodies and consumer organizations). Secondary material is used for describing institutional conditions for consumer trust and the market situation. The results suggest that the idea of consumer trust is associated with the reputation of suppliers, stable quality and taste of their products, and reliable food information. Being a subjectively constructed state connected to the act of acceptance, consumer trust results in positive buying decisions and stable preferences in the food market. The consumers' strategies that aim at safe food choices refer to repetitive interactions with reliable market actors that free them from constant consideration in the marketplace. Trust in food is highly mediated by trust in institutions involved in the food system. The analysis reveals a clear pattern of disbelief in the efficiency of institutional food control. The study analyses this as a reflection of "total distrust" that appears to be a dominant mood in many contexts of modern Russia. However, the interviewees emphasize the state's decisive role in suppressing risks in the food market. Also, the findings are discussed with reference to the consumers' possibilities of personal control over food risks. Three main responses to a risky food situation are identified: the reflexive approach, the traditional approach, and the fatalistic approach.

Food biotechnologies in Italy: a social psychological study

This dissertation presents an analysis of the representations of food biotechnologies in Italy. The thesis uses the analysis of discourse to illustrate the articulated ways in which representations are instantiated in different contexts. The theoretical thrust of the work resides in its discussion of the basic tenets of both Social Representations Theory and Discursive Psychology. The thesis offers a detailed description of the two frameworks; affinities and difference are highlighted, and a serious effort is made to develop an integrated set of theoretical resources to answer the research questions. The thesis proposes to combine a discursive methodology with Social Representations Theory. After a description of the relevant legislative framework follows an illustration of the categories used for the textual analysis. The study proposes the textual analysis of the following data: the first declaration issued by a small Italian council rejecting biotechnologies; four texts which focus on positions taken by the Catholic Church in the matter of food biotechnologies; several transcripts from a public debate in a small community of the north west of Italy. The latter study, which included an ethnographic dimension, focuses on recordings from interviews, a focus group, a public meeting and newspaper articles. Particular attention is paid to ideological representations and to the relevance of citizenship and governance to debates about food biotechnologies.

Sound Velocity Anomaly at the Mott Transition: Application to Organic Conductors and V2O3

Close to the Mott transition, lattice degrees of freedom react to the softening of electron degrees of freedom. This results in a change of lattice spacing, a diverging compressibility, and a critical anomaly of the sound velocity. These effects are investigated within a simple model, in the framework of dynamical mean-field theory. The results compare favorably to recent experiments on the layered organic-conductor kappa-(BEDT-TTF)(2)Cu[N(CN)(2)]Cl. We predict that effects of a similar magnitude are expected for V2O3, despite the much larger value of the elastic modulus of this material.

How Can Sustainable Agricultural Systems Promote Food Security in a Changing Climate?

A theoretical framework of the link between climate change, rural development, sustainable agriculture, poverty, and food security is presented. Some options to respond to climate change are described. Current knowledge and potential effects on agricultural productivity is discussed. Necessary conditions for successful adaptation includes secured property rights to land, institutions that make market access possible and credit possibilities. The options of mitigation and enhanced adaptive capacity and the requirements for their implementation are discussed.

Two ex situ fungal technologies to treat contaminated soil

Wood-degrading fungi are able to degrade a large range of recalcitrant pollutants which resemble the lignin biopolymer. This ability is attributed to the production of lignin-modifying enzymes, which are extracellular and non-specific. Despite the potential of fungi in bioremediation, there is still an understanding gap in terms of the technology. In this thesis, the feasibility of two ex situ fungal bioremediation methods to treat contaminated soil was evaluated. Treatment of polycyclic aromatic hydrocarbons (PAHs)-contaminated marsh soil was studied in a stirred slurry-phase reactor. Due to the salt content in marsh soil, fungi were screened for their halotolerance, and the white-rot fungi Lentinus tigrinus, Irpex lacteus and Bjerkandera adusta were selected for further studies. These fungi degraded 40 - 60% of a PAH mixture (phenanthrene, fluoranthene, pyrene and chrysene) in a slurry-phase reactor (100 ml) during 30 days of incubation. Thereafter, B. adusta was selected to scale-up and optimize the process in a 5 L reactor. Maximum degradation of dibenzothiophene (93%), fluoranthene (82%), pyrene (81%) and chrysene (83%) was achieved with the free mycelium inoculum of the highest initial biomass (2.2 g/l). In autoclaved soil, MnP was the most important enzyme involved in PAH degradation. In non-sterile soil, endogenous soil microbes together with B. adusta also degraded the PAHs extensively, suggesting a synergic action between soil microbes and the fungus. A fungal solid-phase cultivation method to pretreat contaminated sawmill soil with high organic matter content was developed to enhance the effectiveness of the subsequent soil combustion. In a preliminary screening of 146 fungal strains, 28 out of 52 fungi, which extensively colonized non-sterile contaminated soil, were litter-decomposing fungi. The 18 strains further selected were characterized by their production of lignin-modifying and hydrolytic enzymes, of which MnP and endo-1,4-β-glucanase were the main enzymes during cultivation on Scots pine (Pinus sylvestris) bark. Of the six fungi selected for further tests, Gymnopilus luteofolius, Phanerochaete velutina, and Stropharia rugosoannulata were the most active soil organic matter degraders. The results showed that a six-month pretreatment of sawmill soil would result in a 3.5 - 9.5% loss of organic matter, depending on the fungus applied. The pretreatment process was scaled-up for a 0.56 m3 reactor, in which perforated plastic tubes filled with S. rugosoannulata growing on pine bark were introduced into the soil. The fungal pretreatment resulted in a soil mass loss of 30.5 kg, which represents 10% of the original soil mass (308 kg). Despite the fact that Scots pine bark contains several antimicrobial compounds, it was a suitable substrate for fungal growth and promoter of the production of oxidative enzymes, as well as an excellent and cheap natural carrier of fungal mycelium. This thesis successfully developed two novel fungal ex situ bioremediation technologies and introduce new insights for their further full-scale application. Ex situ slurry-phase fungal reactors might be applied in cases when the soil has a high water content or when the contaminant bioavailability is low; for example, in wastewater treatment plants to remove pharmaceutical residues. Fungal solid-phase bioremediation is a promising remediation technology to ex situ or in situ treat contaminated soil.

Thermal Conductivities of Organic Liquids-A New Correlation.

A new equation for predicting the thermal conductivities of organic liquids using dimension-less analysis is given. The equation (Equation Presented) correlates 51 different liquids tested within 11% average error and 17% standard deviation. A comparison of the proposed equation with the available correlations and its application to some industrially important liquids show that this equation can be safely used to calculate the thermal conductivities at 20°C. and 1 atm. pressure for organic liquids of known molecular weight. Cp and ΔHv - the only two parameters for which experimental values must be known for making use of this equation - can be calculated using other well known correlations. The proposed equation is not applicable to inorganic liquids.

Effect of some organic acids on leaf phosphatase from French beans

1. The common organic acids inhibited leaf phosphatase activity, This effect is mostly due to the hydroxyl groups in them. 2. The less common organic acids, which have only carboxyl groups, did not show any marked inhibitory action on phosphatase activity. 3. The less common organic acids eluted the leaf phosphatase after adsorption on aluminacγ gel to a greater extent than the more common organic acids. 4. The second elution of the purified enzyme from the aluminacγ gel was not possible with the organic acids as it was adsorbed on the gel.

Climate change and agriculture: theory and application of mitigation policies

Agriculture’s contribution to climate change is controversial as it is a significant source of greenhouse gases but also a sink of carbon. Hence its economic and technological potential to mitigate climate change have been argued to be noteworthy. However, social profitability of emission mitigation is a result from factors among emission reductions such as surface water quality impact or profit from production. Consequently, to value comprehensive results of agricultural climate emission mitigation practices, these co-effects to environment and economics should be taken into account. The objective of this thesis was to develop an integrated economic and ecological model to analyse the social welfare of crop cultivation in Finland on distinctive cultivation technologies, conventional tillage and conservation tillage (no-till). Further, we ask whether it would be privately or socially profitable to allocate some of barley cultivation for alternative land use, such as green set-aside or afforestation, when production costs, GHG’s and water quality impacts are taken into account. In the theoretical framework we depict the optimal input use and land allocation choices in terms of environmental impacts and profit from production and derive the optimal tax and payment policies for climate and water quality friendly land allocation. The empirical application of the model uses Finnish data about production cost and profit structure and environmental impacts. According to our results, given emission mitigation practices are not self-evidently beneficial for farmers or society. On the contrary, in some cases alternative land allocation could even reduce social welfare, profiting conventional crop cultivation. This is the case regarding mineral soils such as clay and silt soils. On organic agricultural soils, climate mitigation practices, in this case afforestation and green fallow give more promising results, decreasing climate emissions and nutrient runoff to water systems. No-till technology does not seem to profit climate mitigation although it does decrease other environmental impacts. Nevertheless, the data behind climate emission mitigation practices impact to production and climate is limited and partly contradictory. More specific experiment studies on interaction of emission mitigation practices and environment would be needed. Further study would be important. Particularly area specific production and environmental factors and also food security and safety and socio-economic impacts should be taken into account.

From environmental concerns towards sustainable food provisioning. : Material flow and food consumption scenario studies on sustainability of agri-food systems

Agriculture is an economic activity that heavily relies on the availability of natural resources. Through its role in food production agriculture is a major factor affecting public welfare and health, and its indirect contribution to gross domestic product and employment is significant. Agriculture also contributes to numerous ecosystem services through management of rural areas. However, the environmental impact of agriculture is considerable and reaches far beyond the agroecosystems. The questions related to farming for food production are, thus, manifold and of great public concern. Improving environmental performance of agriculture and sustainability of food production, sustainabilizing food production, calls for application of wide range of expertise knowledge. This study falls within the field of agro-ecology, with interphases to food systems and sustainability research and exploits the methods typical of industrial ecology. The research in these fields extends from multidisciplinary to interdisciplinary and transdisciplinary, a holistic approach being the key tenet. The methods of industrial ecology have been applied extensively to explore the interaction between human economic activity and resource use. Specifically, the material flow approach (MFA) has established its position through application of systematic environmental and economic accounting statistics. However, very few studies have applied MFA specifically to agriculture. The MFA approach was used in this thesis in such a context in Finland. The focus of this study is the ecological sustainability of primary production. The aim was to explore the possibilities of assessing ecological sustainability of agriculture by using two different approaches. In the first approach the MFA-methods from industrial ecology were applied to agriculture, whereas the other is based on the food consumption scenarios. The two approaches were used in order to capture some of the impacts of dietary changes and of changes in production mode on the environment. The methods were applied at levels ranging from national to sector and local levels. Through the supply-demand approach, the viewpoint changed between that of food production to that of food consumption. The main data sources were official statistics complemented with published research results and expertise appraisals. MFA approach was used to define the system boundaries, to quantify the material flows and to construct eco-efficiency indicators for agriculture. The results were further elaborated for an input-output model that was used to analyse the food flux in Finland and to determine its relationship to the economy-wide physical and monetary flows. The methods based on food consumption scenarios were applied at regional and local level for assessing feasibility and environmental impacts of relocalising food production. The approach was also used for quantification and source allocation of greenhouse gas (GHG) emissions of primary production. GHG assessment provided, thus, a means of crosschecking the results obtained by using the two different approaches. MFA data as such or expressed as eco-efficiency indicators, are useful in describing the overall development. However, the data are not sufficiently detailed for identifying the hot spots of environmental sustainability. Eco-efficiency indicators should not be bluntly used in environmental assessment: the carrying capacity of the nature, the potential exhaustion of non-renewable natural resources and the possible rebound effect need also to be accounted for when striving towards improved eco-efficiency. The input-output model is suitable for nationwide economy analyses and it shows the distribution of monetary and material flows among the various sectors. Environmental impact can be captured only at a very general level in terms of total material requirement, gaseous emissions, energy consumption and agricultural land use. Improving environmental performance of food production requires more detailed and more local information. The approach based on food consumption scenarios can be applied at regional or local scales. Based on various diet options the method accounts for the feasibility of re-localising food production and environmental impacts of such re-localisation in terms of nutrient balances, gaseous emissions, agricultural energy consumption, agricultural land use and diversity of crop cultivation. The approach is applicable anywhere, but the calculation parameters need to be adjusted so as to comply with the specific circumstances. The food consumption scenario approach, thus, pays attention to the variability of production circumstances, and may provide some environmental information that is locally relevant. The approaches based on the input-output model and on food consumption scenarios represent small steps towards more holistic systemic thinking. However, neither one alone nor the two together provide sufficient information for sustainabilizing food production. Environmental performance of food production should be assessed together with the other criteria of sustainable food provisioning. This requires evaluation and integration of research results from many different disciplines in the context of a specified geographic area. Foodshed area that comprises both the rural hinterlands of food production and the population centres of food consumption is suggested to represent a suitable areal extent for such research. Finding a balance between the various aspects of sustainability is a matter of optimal trade-off. The balance cannot be universally determined, but the assessment methods and the actual measures depend on what the bottlenecks of sustainability are in the area concerned. These have to be agreed upon among the actors of the area