清淤底泥处置中添加粉煤灰/炉渣对重金属生物有效性及毒性的影响

在清淤底泥中添加碱性粉煤灰、燃煤炉渣进行钝化处理后,通过浸出毒性实验、重金属形态分级实验及植物生长实验对底泥基质中重金属的活性及生物有效性进行了研究.结果表明:清淤底泥中添加粉煤灰、燃煤炉渣等碱性物质后显著降低了底泥基质中可溶态重金属含量,其中,交换态、有机结合态Pb、Zn所占比例显著降低;碱性物质的加入缓解了重金属的浸出危害,钝化底泥基质中粉煤灰、炉渣对Cu的稳定率可达90.34%~96.88%;与此同时也抑制了底泥中重金属在植物体内的富集与迁移,降低了重金属的生物有效性.相关性分析表明,底泥基质中交换态重金属含量、浸出浓度、植物茎叶中重金属含量及植物根伸长抑制率之间存在显著正相关关系(p0.01).     

Mercury removal from coal combustion flue gas by modified fly ash

Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.     

Detoxifying PCDD/Fs and heavy metals in fly ash from medical waste incinerators with a DC double arc plasma torch

Medical waste incinerator (MWI) fly ash is regarded as a highly toxic waste because it contains high concentrations of heavy metals anddioxins, including polychlorinateddibenzo-p-dioxins (PCDDs) and polychlorinateddibenzofurans (PCDFs). Therefore fly ash from MWI must be appropriately treated before beingdischarged into the environment. A melting process based on adirect current thermal plasma torch has beendeveloped to convert MWI fly ash into harmless slag. The leaching characteristics of heavy metals in fly ash and vitrified slag were investigated using the toxicity characteristic leaching procedure, while the content of PCDD/Fs in the fly ashes and slags was measured using method 1613 of the US EPA. The experimental results show that thedecomposition rate of PCDD/Fs is over 99% in toxic equivalent quantity value and the leaching of heavy metals in the slag significantlydecreases after the plasma melting process. The produced slag has a compact and homogeneous microstructure withdensity of up to2.8 g/cm3 .     

Effects of solution chemistry on arsenic(Ⅴ) removal by low-cost adsorbents

Natural and anthropogenic arsenic （As） contamination of water sources pose serious health concerns, especially for small communities in rural areas. This study assessed the applicability of three industrial byproducts （coal fly ash, lignite, and green waste compost） as the low-cost adsorbents for As（V） removal under various field-relevant conditions （dissolved oxygen, As（V）/Fe ratio, solution pH, and presence of competing species）. The physico-chemical properties of the adsorbents were characterized by XRD, XRF, FT-IR, and NMR analysis. Batch experiments demonstrated that coal fly ash could provide effective As（V） removal （82.1%-95%） because it contained high content of amorphous iron/aluminium hydroxides for As（V） adsorption and dissolvable calcium minerals for calcium arsenate precipitation. However, the addition of lignite and green waste compost was found unfavourable since they hindered the As（V） removal by 10%-42% possibly due to dissolution of organic matter and ternary arsenate-iron-organic matter complexes. On the other hand, higher concentrations of dissolved iron （comparing As（V）/Fe ratios of 1：1 and 1：10） and dissolved oxygen （comparing 0.2 and 6 mg/L） only marginally enhanced the As（V） removal at pH 6 and 8. Thus, addition of dissolved iron, water aeration, or pH adjustment became unnecessary because coal fly ash was able to provide effective As（V） removal under the natural range of geochemical conditions. Moreover, the presence of low levels of background competing （0.8 or 8 mg/L of humic acid, phosphate, and silicate） imposed little influence on As（V） removal, possibly because the high adsorption capacity of coal fly ash was far from exhaustion. These results suggested that coal fly ash was a potentially promising adsorbent that warranted further investigation.     

湿法预处理对垃圾焚烧飞灰中重金属的形态及风险影响研究

以某典型城市生活垃圾焚烧飞灰为研究对象,采用X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）和电感耦合等离子体光谱仪（ICP）测定了焚烧飞灰的主要成分、矿物学组成和重金属含量,探讨了湿法预处理工艺对飞灰的化学组成、矿物学形态、化学形态及风险水平的影响.结果表明,飞灰的主要化学组成为O、Ca、Cl、Na、K等,占飞灰总质量的93.54％,其次含有0.04％ ～0.68％的Zn、Pb、Cu、Cr等微量重金属元素;经过湿法预处理,飞灰中可溶性氯盐具有较好的去除效果,且几乎所有重金属元素的不稳定形态（弱酸提取态和可还原态）比例都有一定程度的减少,有效降低了重金属的毒性、生物有效性及环境风险水平.本研究有助于降低焚烧飞灰的环境风险和探寻其资源化的有效途径.     

氯化铜催化二噁英生成实验及指纹特性分析

氯化铜被认为是对二■英(PCDD/F)生成促进作用最强的金属催化剂,温度和氧气含量是影响其催化二■英生成的关键因素.本文选取250～550℃间8个不同温度点及0～20%间4种不同氧气含量,系统性地研究了温度和氧气含量对含氯化铜模拟飞灰(MFA)生成二■英的影响,并通过分析指纹特性探讨二■英的生成路径和机理.结果发现,290～350℃之间二■英生成量较高,且在290℃时二■英总量达到最大值;氧气含量为10%时二■英生成量达到最高.研究二■英同分异构体分布可从分子层面为研究其生成路径和机理提供重要信息,因此,本文分析了四至八氯代PCDD/F的全部异构体的分布.结果表明,在本文所选取的温度和氧含量范围内,温度对二■英生成路径的影响高于氧气含量.最后,重点讨论了2,3,7,8位氯取代的17种有毒异构体的分布随温度和氧气的变化情况及生成路径.利用主成分分析法(PCA)证实了氯化铜催化二■英从头合成过程中存在经由氯酚路径生成的异构体,并讨论了不同工况下氯酚路径对二■英生成的影响.     

垃圾焚烧飞灰中Pb及特征药剂稳定化处理

筛选几种重金属药剂用于稳定垃圾焚烧飞灰,以重金属Pb为处理目标,通过单一或复配形式研究药剂的稳定效果并采用红外光谱（FT-IR）和X射线衍射（XRD）分析重金属稳定机理.结果表明,有机药剂稳定后Pb的螯合率高于无机药剂,投加质量分数为2%二乙基DTC能使Pb的浸出满足危险废物填埋污染控制标准（GB 18598-2019）要求,然而5%的硫化钠和磷酸二氢钠稳定后Pb的浸出浓度仍不达标;药剂处理后,Pb的部分不稳定态被转化为稳定态,且相比于无机药剂,有机药剂稳定后Pb的残渣态占比更高,抗酸碱能力更强;无机药剂处理后Pb的浸出性与养护时间成负相关,而有机药剂则由于特征官能团的氧化等因素而成正相关.成本核算结果表明,0.9%二乙基DTC和3%磷酸二氢钠复合药剂稳定飞灰在满足GB 18598-2019要求的基础上,成本相比于单一二乙基DTC处理降低26.72%.复合药剂处理后,飞灰中出现了N、S、P的特征吸收峰,重金属主要以螯合、沉淀作用稳定,同时整个体系的矿物组成并未发生改变,但结晶相的吸收峰强度明显减弱.     

调理剂对磷镉富集土壤中两种元素交互作用的影响

以磷镉富集的农业土壤（总Cd：0.94mg·kg^-1和全P：0.86g·kg^-1）为研究对象,按照湖北地区中稻生育期及至下茬作物播种期的时长进行室内培养试验,探究生物质炭（BC）、钙镁磷肥（CMP）和粉煤灰（FA）影响下土壤磷与镉的生物有效性、二者形态变化及其耦合作用效应.结果表明：①培养至140d时,添加调理剂处理土壤有效磷含量与未添加调理剂的对照土壤相比均显著增加,有效磷水平可达22.47~37.81mg·kg^-1,在不额外施用磷肥条件下可满足水稻最适生长需求,且添加BC处理的效果最佳.②供试土壤中的磷主要为无机正磷酸盐,且不同形态无机磷含量在调理剂作用下均有所提高,并随着时间土壤中固定态的O-P和Ca₁₀-P逐渐向活性较高的Ca₂-P、Ca₈-P、Al-P和Fe-P形态转变.③添加调理剂处理土壤有效态Cd含量在对照处理基础上显著降低8.74%~17.48%,这与3种调理剂对土壤pH的提高作用相关联.与此同时,添加调理剂的处理与对照相比,可交换态Cd显著降低,碳酸盐结合态Cd和残渣态Cd均有所提高,这与土壤有机质在BC的促进效应下,其表面富含的活性基团能够与Cd²⁺吸附螯合有关.结果初步证明,3种调理剂均能实现供试磷镉富集土壤中磷活化和镉钝化的双重功能,并以生物质炭和钙镁磷肥效果为佳,其效果可覆盖整个水稻生长时段并可延续至其下茬作物播种期.     

Adsorptive removal and recovery of the azo dye Eriochrome Black T

Bottom ash and de-oiled soya have been evaluated as potential adsorbents for the removal of a water soluble azo dye. The characterization of the adsorbents has been performed using infrared spectroscopy and differential thermal analysis. A batch of adsorption method has been adopted for studying the effects of pH, adsorbate concentration, and particle size on the adsorption process. The experimental data were tested using Langmuir, Freundlich, Tempkin, and Dubinin–Radushkevich isotherms and their parameter constants were determined. The thermodynamics showed that the process is spontaneous and exothermic. The kinetic studies revealed that the adsorption process follows first-order kinetics. A fixed-bed adsorption experiment resulted in 89% and 94% saturation of bottom ash and de-oiled soya, respectively, indicating that both adsorbents can be potentially economical.