Thermolysis of 2,4,6-trichlorophenol chemisorbed on aluminium oxides as example of fly ash mediated surface catalysis reaction in PCDD/PCDF formation

The influence of aluminium cation as a strong electrophilic centre on the thermolysis of chlorophenols chemisorbed on Al(OH)₃ surface was investigated. If thermolysis is carried out at 300 °C the spontaneous rupture of the bond between aluminium and oxygen of phenol takes place in the temperature range of 260–280 °C. The thermolysis of chlorophenoxy aluminium compounds occurs through homolytic and heterolytic bond cleavage. In the case of heterolytic cleavage the leaving chlorophenoxy anion causes a simultaneous formation of the aluminium cation, which is the driving force for the rearrangement of the unstable intermediate. By homolytic cleavage of the Al–O bond the chlorophenoxy radical is formed. The isolation of reaction products of the thermolysis of the system Al(OH)₃/2,4,6-trichlorophenol gave five isomers of dimeric compounds of resonance stabilised 2,4,6-trichlorophenoxy radical. The compounds are stable in nonaqueous, aprotic solution, but they are very sensitive to acid catalysis. They quickly transform into aromatic hydroxydiphenyl ethers. The process of dechlorination and aromatisation of cyclohexadienone dimers gives PCDD/PCDF.     

Characterizing As(III,V) adsorption by soils surrounding ash disposal facilities

Leachate derived from unlined coal ash disposal facilities is a potential anthropogenic source of arsenic to the environment. To establish a theoretical framework for predicting attenuation of arsenic by soils subject to ash landfill leachate, which is typically enriched in calcium and sulfate, the adsorption of As(V) and As(III) was characterized from 1 mM CaSO₄ for 18 soils obtained down-gradient from three ash landfill sites and representing a wide range in soil properties. As(V) consistently exhibited an order of magnitude greater adsorption than As(III). As(V) adsorption was best described by coupling pH with 15 s DCB-Fe (R² = 0.851,  = 0.001), although pH coupled to clay, DCB-Fe, or DCB-Al also generated strong correlations. For As(III), pH coupled to Ox–Fe (R² = 0.725,  = 0.001) or Ox–Fe/Al (R² = 0.771,  = 0.001) provided the best predictive relationships. Ca²⁺ induced increases in As(V) adsorption whereas sulfate suppressed both As(V) and As(III) adsorption. Attenuation of arsenic from ash leachate agreed well with adsorption measured from 1 mM CaSO₄ suggesting that the use of 1 mM CaSO₄ in laboratory adsorption tests is a reasonable approach for estimating arsenic behavior in soils surrounding ash landfills. We also showed that the impact of leachate-induced changes in soil pH over time may not be significant for As(V) adsorption at pH < 7; however, As(III) adsorption may be impacted over a wider pH range especially if phyllosilicate clays contribute significantly to adsorption. The benefits and limitations of predicting arsenic mobility using linearized adsorption coefficients estimated from nonlinear adsorption isotherms or from the relationships generated in this study are also discussed.     

Ancient manuring practices pollute arable soils at the St Kilda World Heritage Site, Scottish North Atlantic

The impact of ancient fertilization practices on the biogeochemistry of arable soils on the remote Scottish island of Hirta, St Kilda was investigated. The island was relatively unusual in that the inhabitants exploited seabird colonies for food, enabling high population densities to be sustained on a limited, and naturally poor, soil resource. A few other Scottish islands, the Faeroes and some Icelandic Islands, had similar cultural dependence on seabirds. Fertilization with human and animal waste streams (mainly peat ash and bird carcases) on Hirta over millennia has led to over-deepened, nutrient-rich soils (plaggen). This project set out to examine if this high rate of fertilization had adversely impacted the soil, and if so, to determine which waste streams were responsible. Arable soils were considerably elevated in Pb and Zn compared to non-arable soils. Using Pb isotope signatures and analysis of the waste streams, it was determined that this pollution came from peat and turf ash (Pb and Zn) and from bird carcases (Zn). This was also confirmed by ¹³C and ¹⁵N analysis of the profiles which showed that soil organic matter was highly enriched in marine-derived C and N compared to non-arable soils. The pollution of such a remote island may be typical of other ‘bird culture’ islands, and peat ash contamination of marginal arable soils at high latitudes may be widespread in terms of geographical area, but less intense at specific locations due to lower population densities than on Hirta.     

Management of Lignite Fly Ash for Improving Soil Fertility and Crop Productivity

Lignite fly ash (LFA), being alkaline and endowed with excellent pozzolanic properties, a silt loam texture, and plant nutrients, has the potential to improve soil quality and productivity. Long-term field trials with groundnut, maize, and sun hemp were carried out to study the effect of LFA on growth and yield. Before crop I was sown, LFA was applied at various doses with and without press mud (an organic waste from the sugar industry, used as an amendment and source of nutrients). LFA with and without press mud was also applied before crops III and V were cultivated. Chemical fertilizer, along with gypsum, humic acid, and biofertilizer, was applied in all treatments, including the control. With one-time and repeat applications of LFA (with and without press mud), yield increased significantly (7.0–89.0%) in relation to the control crop. The press mud enhanced the yield (3.0–15.0%) with different LFA applications. The highest yield LFA dose was 200 t/ha for one-time and repeat applications, the maximum yield being with crop III (combination treatment). One-time and repeat application of LFA (alone and in combination with press mud) improved soil quality and the nutrient content of the produce. The highest dose of LFA (200 t/ha) with and without press mud showed the best residual effects (eco-friendly increases in the yield of succeeding crops). Some increase in trace- and heavy-metal contents and in the level of γ-emitters in soil and crop produce, but well within permissible limits, was observed. Thus, LFA can be used on a large scale to boost soil fertility and productivity with no adverse effects on the soil or crops, which may solve the problem of bulk disposal of fly ash in an eco-friendly manner.     

Ecophysiological Competence of <Emphasis Type="Italic">Populus alba</Emphasis> L., <Emphasis Type="Italic">Fraxinus angustifolia</Emphasis> Vahl., and <Emphasis Type="Italic">Crataegus monogyna</Emphasis> Jacq. Used in Plantations for the Recovery of Riparian Vegetation

In many semi-arid environments of Mediterranean ecosystems, white poplar (Populus alba L.) is the dominant riparian tree and has been used to recover degraded areas, together with other native species, such as ash (Fraxinus angustifolia Vahl.) and hawthorn (Crataegus monogyna Jacq.). We addressed three main objectives: (1) to gain an improved understanding of some specific relationships between environmental parameters and leaf-level physiological factors in these riparian forest species, (2) to compare the leaf-level physiology of these riparian species to each other, and (3) to compare leaf-level responses within native riparian plots to adjacent restoration plots, in order to evaluate the competence of the plants used for the recovery of those degraded areas. We found significant differences in physiological performance between mature and young white poplars in the natural stand and among planted species. The net assimilation and transpiration rates, diameter, and height of white poplar plants were superior to those of ash and hawthorn. Ash and hawthorn showed higher water use efficiency than white poplar. White poplar also showed higher levels of stomatal conductance, behaving as a fast-growing, water-consuming species with a more active gas exchange and ecophysiological competence than the other species used for restoration purposes. In the restoration zones, the planted white poplars had higher rates of net assimilation and water use efficiency than the mature trees in the natural stand. We propose the use of white poplar for the rapid restoration of riparian vegetation in semi-arid Mediterranean environments. Ash and hawthorn can also play a role as accompanying species for the purpose of biodiversity.     

贵州典型电厂粉煤灰的放射性安全评估

贵州是华南最重要的煤电和粉煤灰生产省份,粉煤灰的放射性安全评估是综合利用的基础。对贵州不同产煤区域典型电厂粉煤灰进行了放射性核素比活度测定并根据国标GB6566-2001进行了安全性评估,结果表明:西部纳雍电厂粉煤灰内照射指数IRa和外照射指数Iγ均较低,使用范围不受限制;中部大方、金沙电厂和东部黔东电厂粉煤灰I_(Ra)较低而I_γ接近限值,可以作为建筑主体材料(其中大方一级灰仅限于空心率大于25%的主体材料)和A类装修材料;北部桐梓和二郎电厂粉煤灰I_(Ra)和I_γ均超出限值,分别可作为B类和C类装修材料,作为建筑主体材料应严格控制掺量比例。综合本次研究和前人数据,确证了粉煤灰中U、Th含量和相关放射性核素比活度具有良好相关性,推导了利用粉煤灰U、Th含量(C_U,C_(Th),×10~(-6))进行快速评估的经验公式:I_(Ra)=0. 0616×C_U+0. 0049;I_γ=0. 0341×C_U+0. 0159×C_(Th)+0. 0517。     

循环流化床锅炉脱硫灰熔融固化特性研究

为了解决循环流化床锅炉脱硫灰堆存带来的二次污染问题,同时为了将固硫灰能够资源化利用,采用高温熔融技术对脱硫灰进行熔融固化处理,在对熔渣的物相变化、组成变化、密度、重金属、浸出量等特性进行分析的基础上,还研究了冷却方式对熔渣性质的影响。实验结果表明:经熔融处理后,脱硫灰的体积大幅度减小,有害重金属得到了有效固化,同时不同冷却方式能够得到不同性质的熔渣产品。证明熔融固化技术可以实现循环流化床锅炉脱硫灰的减量化、无害化以及资源化利用。     

综合治理立窑烟尘和有害气体的组合分离器研究

从分析现行技术治理立窑烟尘现状着手,研制一种立窑烟尘和有害气体综合治理的新技术和新设备--双重调节分流口式组合分离器.实验结果表明,双重调节分流口式组合分离器有较高的捕集细粉能力,用近于旋风收尘器的成本,收到近于袋收尘的除尘效果,再施予一定的荷湿条件,能综合治理立窑烟尘和有害气体.     

酸碱回收对粉煤灰合成沸石性能的影响

针对粉煤灰合成沸石合成成本较高及废酸碱外排污染环境的问题,对粉煤灰合成人工沸石工艺中废酸碱回收的可行性及其对合成沸石产品性能的影响进行了试验研究,研究设置3个废酸碱回收利用比例条件(1:1,2:1,3:1),其他合成条件与初始粉煤灰合成沸石完全相同.利用SEM、XRD、BET等技术对合成产品进行表征,结果表明回收酸合成沸石(WAC-ZFA)、回收碱合成沸石(WAL-ZFA)表面存在大量孔隙结构,XRD图谱也存在尖锐的沸石衍射峰,表征结果与粉煤灰合成沸石(ZFA)相似;在BET方面,与ZFA相比,WAC-ZFA有所下降,而WAL-ZFA明显增大;废碱回收比例对合成沸石除氨的效果影响不大,而废酸回收比例对合成沸石除氨的效果影响较明显,综合考虑,建议在实际生产中废酸回收比例宜≤1:1,废碱回收比例宜≤3:1.     

粉煤灰改性及其在废水处理中的应用现状研究

粉煤灰是煤高温燃烧后的产物,在形成过程中形成了一定的多孔结构和较大的比表面积,具有一定的吸附能力,可以作为水处理材料。但由于原性粉煤灰吸附性能有限,对水中污染物的去除率较低,不能满足水处理的实际要求。因此,研究热点集中在对粉煤灰进行改性处理,增加粉煤灰中的活性组分,增大粉煤灰的比表面积,提高其性能,从而增强其对废水处理的效果。粉煤灰在废水处理领域的应用,增加了粉煤灰的综合利用途径,同时以废治废,符合节能环保政策。笔者对粉煤灰的改性方法及其在废水处理中的应用现状进行了总结,以期对粉煤灰的在废水处理中的综合利用提供参考。