氨对垃圾焚烧飞灰浸出特性的影响及地球化学模拟

垃圾焚烧飞灰可能因为选择性非催化还原法(SNCR)脱硝过程中氨泄漏、垃圾携带的渗滤液受热挥发等原因而吸附氨.本研究中采用人为添加氨水,在pH为3.66～12.44范围内,研究氨对飞灰中溶解性有机碳(DOC)和重金属浸出的影响,并利用地球化学模拟软件Visual MINTEQ从金属化学形态分布上分析氨对飞灰浸出的影响机制.结果表明,DOC在pH>9和有高浓度氨(≥1 357 mg·L-1)存在时,其浸出量大幅增加,而在浸出液中氨的水平不高于537 mg·L-1时则受氨的影响很小;在pH<6时,飞灰中各金属主要以自由态的金属离子和金属-氯络离子形态大量溶出,且受氨的影响较小;而在pH为8～12的碱性环境中和氨浓度较高时(≥3 253 mg·L-1),氨与金属生成了可溶性的金属-氨配合物,能显著增加Cd、Cu、Ni、Zn的浸出,且在pH=9附近时浸出量达到最大值,但氨对Al和Pb的浸出影响甚微;在pH>12时,Cd、Cu、Ni、Zn主要以羟基金属离子形式存在.在氨浓度为3 253 mg·L-1时,通过利用Visual MINTEQ模拟浸出值与试验数据的对比,发现Al、Pb、Zn的浸出主要由溶解/沉淀模型控制,而Cd、Cu、Ni由溶解/沉淀模型和表面吸附反应模型同时控制,且Visual MINTEQ模型能较好地预测飞灰中Al、Cu、Pb、Zn的浸出特性.     

Dioxin screening in fish product by pattern recognition of biomarkers

Two alternative, cost- and time-effective dioxin screening methods relying on two categories of potential lipid biomarkers were investigated. A dioxin range varying from 1.1 to 47.1 pg PCDD/F TEQ-WHO/g lipid using 64 fish meal samples was used for model calibration. The methods were based on multivariate models using either (1) fatty acid composition monitored by GC-FID or (2) fluorescence landscape signals analysed using the PARAFAC model and in both cases predicting dioxin content as pgPCDD/F TEQ-WHO/g lipid. In both cases, Partial Least Squares (PLS) regression was performed for predicting the dioxin content of a sample. The GC-FID data analyses was based on automatic peak alignment and integration, enabling extraction of the area of 140 peaks from the gas chromatograms, as opposed to the 31 fatty acids usually considered for fish oil characterisation. In addition to classic PLS employing the whole dataset for calibration, a two-step local PLS modeling approach was performed based upon an initial selection of k number of calibration samples providing the best match to the prediction sample using a so-called k Nearest Neighbors (kNN) approach, then followed by PLS calibration on these kNN selected samples for dioxin prediction. Fluorescence spectroscopy offers a promising non-invasive and ultra-rapid technique, with less than two minutes analysis time. However, fluorescence spectroscopy using the pattern recognition "kNN-PLS" yielded a correlation of 0.76 (r2) and a high root mean square error of prediction of 11.4 pg PCDD/F TEQ-WHO/g lipid. The predictions were improved when the PLS calibration was performed on all the sample with a root mean square error of prediction of 7.0 pg PCDD/F TEQ-WHO/g lipid. Unfortunately, these results failed to demonstrate the potential of fluorophore monitoring as a screening method. In contrast, the overall best screening performance was obtained with the fatty acid profile, when the kNN-PLS combination employed for pattern recognition (kNN) all the areas of the 140 detected peaks and the PLS regression used the areas of 46 selected peaks. This "kNN-PLS" prediction with three latent variables and based upon the 12 nearest neighbors selected out of the 64 x 2 fatty acid profiles (duplicate analyses), yielded a correlation of 0.85 (r2) and a root mean square error of prediction of 2.1 pg PCDD/F TEQ-WHO/g lipid and resulted in a total analysis time of one and half hour per sample.     

Local and regional variability in snow conditions in northern Finland: A reindeer herding perspective

Weather station measurements were used to force the SNOWPACK snow model and combined with reindeer herders’ experiences to study the local and regional variations in snow conditions in a Finnish reindeer herding area for the 1981–2010 period. Winter conditions varied significantly between the four selected herding districts and between open and forest environments within the districts. The highest snow depths and densities, the thicknesses of ground ice, and the lengths of snow cover period were generally found in the northernmost districts. The snow depths showed the strongest regional coherence, whereas the thicknesses of ground ice were weakly correlated among the districts. The local variation in snow depths was higher than the regional variation and limits for rare or exceptional events varied notably between different districts and environments. The results highlight that forests diversify snow and foraging conditions, e.g., ground ice rarely forms simultaneously in different environments. Sufficient and diverse forest pastures are important during the critical winter season if reindeer herding is pursued on natural grazing grounds also in the future.     

Decline of woody vegetation in a saline landscape in the Groundnut Basin,Senegal

Several studies have documented that vegetation in the Sahel is highly dynamic and is affected by the prevailing climatic conditions, as well as by human use of the areas. However, little is known about vegetation dynamics in the large saline areas bordering the rivers of West Africa. Combining satellite imagery, the perception of local people and botanical information, this study investigated the vegetation dynamics and the drivers of vegetation changes in Fatick Province, Senegal. Satellite images showed a change in vegetation composition, i.e., a loss of tree cover and an increase in shrub cover, herbaceous cover and tans (highly saline areas with sparse vegetation). Although the trend was the same, the three villages had different vegetation histories. A survey of the woody vegetation showed that shrubs and young trees were dominating with relatively few large trees. Local people perceived a general decline of woody plants from 1993 to 2013. Among 60 species mentioned by local people, 90 % were declining and 10 % increasing. Together the three methods documented a decrease in density and diversity of the woody vegetation, mainly influenced by salinity and land use. The large numbers of young trees indicate a potential for regeneration of some, but not all, tree species. As many tree species appreciated by local people were reported to be declining, local communities have experienced a reduction of their natural resources. Based on villagers’ recommendations for improved vegetation management, we discuss possible contributions including reforestation, desalinization and environmental protection for restoration of the vegetation.     

Assessment of long-term leaching from waste incineration air-pollution-control residues

Assessment of long-term leaching from MSWI air-pollution-control (APC) residues is discussed with respect to use in environmental impact assessment, such as life-cycle assessment (LCA). A method was proposed for estimating leaching as a function of the liquid-to-solid (L/S) ratio in a long-term perspective (L/S 5000l/kg). Data for changes in residue pH as a function of L/S was used in combination with pH dependent leaching data to predict leachate concentrations of Al, Ca, Cd, Ba, Mg, Ni, Pb, S, Pb, V and Zn as a function of L/S. Mass balance calculations were used to determine the element fractions leached with respect to L/S. The estimated long-term leaching from a semi-dry residue and a fly ash was compared with short-term leaching determined by batch tests at L/S 10l/kg, both carbonated and non-carbonated versions of the residues were investigated. Generally, very high L/S ratios above 2000l/kg were required to leach 20-30% of the solid contents. However, Ca and S were depleted at L/S 200-900l/kg. The long-term leachate concentrations were found to either remain at the same level as the initial leaching determined by the L/S 10 batch test, or to significantly decrease compared with the initial leaching. Only Al and Zn were found to show higher leachate concentrations at L/S ratios above 3000-5000l/kg. Carbonation generally prolonged the time needed for depletion from the solid residues; however, Ca and S were depleted faster than in the case of non-carbonated residues. This study shows that uncritical use of batch leaching data for assessing the potential leaching is highly problematic, and evaluations of residue disposal should include scenario specific quantification of the long-term leaching.     

Optimal utilization of waste-to-energy in an LCA perspective

Energy production from two types of municipal solid waste was evaluated using life cycle assessment (LCA): (1) mixed high calorific waste suitable for production of solid recovered fuels (SRF) and (2) source separated organic waste. For SRF, co-combustion was compared with mass burn incineration. For organic waste, anaerobic digestion (AD) was compared with mass burn incineration. In the case of mass burn incineration, incineration with and without energy recovery was modelled. Biogas produced from anaerobic digestion was evaluated for use both as transportation fuel and for heat and power production. All relevant consequences for energy and resource consumptions, emissions to air, water and soil, upstream processes and downstream processes were included in the LCA. Energy substitutions were considered with respect to two different energy systems: a present-day Danish system based on fossil fuels and a potential future system based on 100% renewable energy. It was found that mass burn incineration of SRF with energy recovery provided savings in all impact categories, but co-combustion was better with respect to Global Warming (GW). If all heat from incineration could be utilized, however, the two alternatives were comparable for SRF. For organic waste, mass burn incineration with energy recovery was preferable over anaerobic digestion in most impact categories. Waste composition and flue gas cleaning at co-combustion plants were critical for the environmental performance of SRF treatment, while the impacts related to utilization of the digestate were significant for the outcome of organic waste treatment. The conclusions were robust in a present-day as well as in a future energy system. This indicated that mass burn incineration with efficient energy recovery is a very environmentally competitive solution overall.     

Characterization of household waste in Greenland

The composition of household waste in Greenland was investigated for the first time. About 2 tonnes of household waste was sampled as every 7th bag collected during 1 week along the scheduled collection routes in Sisimiut, the second largest town in Greenland with about 5400 inhabitants. The collection bags were sorted manually into 10 material fractions. The household waste composition consisted primarily of biowaste (43%) and the combustible fraction (30%), including anything combustible that did not belong to other clean fractions as paper, cardboard and plastic. Paper (8%) (dominated by magazine type paper) and glass (7%) were other important material fractions of the household waste. The remaining approximately 10% constituted of steel (1.5%), aluminum (0.5%), plastic (2.4%), wood (1.0%), non-combustible waste (1.8%) and household hazardous waste (1.2%). The high content of biowaste and the low content of paper make Greenlandic waste much different from Danish household waste. The moisture content, calorific value and chemical composition (55 elements, of which 22 were below detection limits) were determined for each material fraction. These characteristics were similar to what has been found for material fractions in Danish household waste. The chemical composition and the calorific value of the plastic fraction revealed that this fraction was not clean but contained a lot of biowaste. The established waste composition is useful in assessing alternative waste management schemes for household waste in Greenland.     

Energy recovery from waste incineration: Assessing the importance of district heating networks

Municipal solid waste incineration contributes with 20% of the heat supplied to the more than 400 district heating networks in Denmark. In evaluation of the environmental consequences of this heat production, the typical approach has been to assume that other (fossil) fuels could be saved on a 1:1 basis (e.g. 1 GJ of waste heat delivered substitutes for 1 GJ of coal-based heat). This paper investigates consequences of waste-based heat substitution in two specific Danish district heating networks and the energy-associated interactions between the plants connected to these networks. Despite almost equal electricity and heat efficiencies at the waste incinerators connected to the two district heating networks, the energy and CO₂ accounts showed significantly different results: waste incineration in one network caused a CO₂ saving of 48 kg CO₂/GJ energy input while in the other network a load of 43 kg CO₂/GJ. This was caused mainly by differences in operation mode and fuel types of the other heat producing plants attached to the networks. The paper clearly indicates that simple evaluations of waste-to-energy efficiencies at the incinerator are insufficient for assessing the consequences of heat substitution in district heating network systems. The paper also shows that using national averages for heat substitution will not provide a correct answer: local conditions need to be addressed thoroughly otherwise we may fail to assess correctly the heat recovery from waste incineration.     

Influence of test conditions on solubility controlled leaching predictions from air-pollution-control residues.

Leaching of Al, Ca, Mg, Si, S, Ba, Sr, Mo, Zn, Cd, Pb, and Cu from waste incineration air-pollution-control (APC) residues was investigated. Real-life conditions, i.e. removal of readily soluble compounds and longer equilibration time, were considered. Three different pH-static leaching experiments evaluating the importance of salt level and equilibration time were performed: (i) 48-h test on untreated APC residue samples, (ii) 48-h test on washed residue samples, and finally (iii) a 172-h test on washed residue samples. Experimental data were evaluated by geochemical modelling to identify potential solubility controlling minerals. For some elements (Al, Ca, Mg, Si, S, Mo, Zn, Cd, and Cu) the same controlling minerals were suggested regardless of the equilibration period or untreated/washed character of the tested material, whereas leaching of other elements (Ba, Sr) was far better described by considering a longer equilibration time, thereby pointing out the kinetic effects. Finally, a significant fraction of total lead (57%) was found to be rather mobile in the initial stage of leaching. Both pre-washing of the residues and longer equilibration times were shown to be simple yet useful methods to identify mineral phases that could control the release of constituents after the removal of readily soluble compounds in the initial stage of leaching.