Effects of sulfur on variations in the chemical speciation of heavy metals from fly ash glass

● A higher sulfur content reduced the curing rate of Cr in glass. ● Depolymerization increased the amounts of heavy metals in the carbonate bound state. ● Reducing the CaO/SiO₂ ratio increased the proportion of stable heavy metals. This work designed a new CaO-Al₂O₃-SiO₂-SO₃ glass for the immobilization of multiple heavy metals found in dechlorinated fly ash having high amounts of calcium and sulfur. Increasing the (CaO + SO₃)/SiO₂ mass ratio (M(CS/S)) from 0.28 to 0.85 was found to lower the proportions of Mn, Ni and Zn in an unstable state, while an M(CS/S) ratio of 0.51 gave the lowest proportions of unstable Cr and Pb. Decreasing the degree of polymerization of the glassy network increased the proportions of Mn, Cr, Ni, Pb and Zn in the carbonate bound state. The leaching out of metals in this state was the primary cause of degradation of Q³ structural units in the glassy network. The amount of Mn in the iron-manganese oxide bound state was increased by increasing the number of Q² units in the silicate network. Decreasing the CaO/SiO₂ mass ratio (M(C/S)) raised the proportions of Mn, Ni and Zn in the unstable state. An M(C/S) value of 0.43 lowered the proportions of unstable Cr and Pb. A principal components analysis determined that the leaching of toxic heavy metals from the glass was primarily related to the proportions of these metals in the unstable state while there were no evident correlations between leaching and the proportions in stable states.     

Trace elemental characterization of fly ash

The purpose of this study was to determine heavy metal concentrations in ash samples taken from the filter of the gas cleaning system of biomass incinerators in Austria. Knowing the concentrations of heavy metals is important for the decision of further treatment or utilization of the ashes. The heavy metals contained in the ashes remain in the bottom ash of the incinerator or leave the incinerator with the off-gas and are collected in the off-gas filter. The amount of the metals in the collected fly ash depends on the composition of the input material. The aim of this study was to examine this influence and compare the results with literature data. For measurement, the fly ash samples were at first dissolved in a microwave digestion unit using nitric acid and hydrochloric acid. Afterwards, 20 metals were analyzed by inductively coupled plasma optical emission spectrometry. Al, Fe, Mg, Mn, and Zn were found in higher concentrations in the fly ash samples. The enrichment factor between the concentrations in the fly ash and the concentrations in the input material was on average in the range of 18.     

Recovery of molybdenum from fly ash by gibbsite

The effectiveness of gibbsite (GB), an amorphous aluminum oxide, for the recovery of Mo(VI) from eluates of fly ash of two coal-fired thermal power stations and of roof tile waste was investigated. Upon the qualitative analysis of an eluate of fly ash, 16 elements were detected. Greater amounts of these elements were eluted under acidic conditions (pH 2) than from the neutral or basic eluate of fly ash. GB was used for the adsorption of Mo(VI). Equilibrium adsorption was reached within 1?min. Optimal solution acidity for the adsorption of Mo(VI) onto GB400 (calcined at 400°C) was pH 2. The main adsorption mechanism was ion exchange with a number of hydroxyl groups of GB400. For repeated ad- and desorption of Mo(VI), GB400 could be used at least four times and the recovery percentage of Mo(VI) with sodium hydroxide solution as eluent surpassed 90%. Our results showed that GB400 was very effective for the recovery of Mo(VI) from fly ash.     

不同粒径垃圾焚烧飞灰中重金属富集特性表征

针对杭州市生活垃圾焚烧飞灰按粒径级别进行其重金属特性表征,主要展开飞灰组成元素和矿物成分、重金属含量分布、以及重金属与飞灰颗粒的微观结合行为等研究.结果表明,＂SiO2-CaO-Al2O3-金属氧化物＂体系构成了重金属的富集载体;Zn、Pb、Cu、Mn、Ni、Cr、Sb等重金属在75—125μm飞灰颗粒中的占有率最高,达52%;Zn、Cu、Cr随着粒径减小其含量显著增加,其它重金属未见此趋势;通过SEM-EDX对飞灰颗粒表面和断面进行扫描电镜观察和面、线扫描元素能谱分析,在飞灰断面发现了更多类型、更密集的重金属分布.通过结合XRF、ICP-MS、SEM-EDX等仪器手段分析飞灰中重金属富集特性,深入探索重金属在飞灰颗粒中富集特征.     

Treatment of dyeing wastewater using coal fly ash as co-coagulant

This article deals with the co-coagulation of dyeing wastewater by coal fly ash using FeSO₄ as coagulant, Benzo Scarlet 4BS and Brilliant Acid Scarlet 3R as the testing dyes. The optimal concentration of FeSO₄ for co-coagulation process is 0.6–0.8?g/L wastewater, and the concentration of fly ash 4–5?g/L. The experimental results show that the co-coagulation process by fly ash helps to improve the color reduction, greatly accelerate the formation and settling of the floc, and reduce the content of the floc. The mechanism for co-coagulation process is discussed and similar effect is obtained when the co-coagulation method is applied for the treatment of the real dyeing wastewater samples.     

Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.     

红枫湖水源地附近粉煤灰堆积场重金属存在形态及静态淋溶规律

酸雨对露天粉煤灰堆积场的淋滤作用导致周围环境产生重金属污染是一种广泛现象.为研究酸雨对贵阳市水源地红枫湖周边一大型粉煤灰堆积场的重金属迁移影响,本文以这一粉煤灰堆积场为研究对象,通过静态淋溶实验探讨了粉煤灰中Cr、Ni、CU、Zn、AS、Cd、Pb等7种重金属元素的含量、存在形态、淋溶时间、堆积时间、粒度对重金属溶出规律的影响.结果表明,粉煤灰中Ni、Cu、Zn、Pb、As和Cd等6种重金属的含量随堆积时间增加而增大,Cr含量变化与上述反之;在淋溶实验中,堆积时间的增加使Cr、Ni、Cu和Zn重金属元素的可溶态减小;在淋溶第28—48天期间,Cr、Ni和Cu元素溶出浓度降低的粒度顺序为细粒度>中粒度和粗粒度、Cd元素溶出浓度降低的粒度顺序为中粒度>粗粒度>细粒度.本研究对红枫湖水源地和周边地下水的重金属防控提供一定的参考依据.     

Efficient removal of heavy metals from electroplating wastewater using polymer ligands

Poly(hydroxamic acid)-poly(amidoxime) chelating ligands were synthesized from poly(methyl acrylate-co-acrylonitrile) grafted acacia cellulose for removing toxic metal ions from industrial wastewaters. These ligands showed higher adsorption capacity to copper (2.80 mmol?g⁻¹) at pH 6. In addition, sorption capacities to other metal ions such as iron, zinc, chromium, and nickel were also found high at pH 6. The metal ions sorption rate (t_1/2) was very fast. The rate of adsorption of copper, iron, zinc, chromium, nickel, cobalt, cadmium and lead were 4, 5, 7, 5, 5, 8, 9 and 11 min, respectively. Therefore, these ligands have an advantage to the metal ions removal using the column technique. We have successfully investigated the known concentration of metal ions using various parameters, which is essential for designing a fixed bed column with ligands. The wastewater from electroplating plants used in this study, having chromium, zinc, nickel, copper and iron, etc. For chromium wastewater, ICP analysis showed that the Cr removal was 99.8% and other metal ions such as Cu, Ni, Fe, Zn, Cd, Pb, Co and Mn removal were 94.7%, 99.2%, 99.9%, 99.9%, 99.5%, 99.9%, 95.6% and 97.6%, respectively. In case of cyanide wastewater, the metal removal, especially Ni and Zn removal were 96.5 and 95.2% at higher initial concentration. For acid/alkali wastewater, metal ions removing for Cd, Cr and Fe were 99.2%, 99.5% and 99.9%, respectively. Overall, these ligands are useful for metal removal by column method from industrial wastewater especially plating wastewater.     

Release of elements from municipal solid waste incineration fly ash

The element-release behavior of municipal solid waste incineration fly ash was explored through leaching test with continuous set-point pH (pH_stat test) and serial single reaction cell (SSRC) tests. First, the relationship between element release and acid neutralizing capacity (ANC) consumption was examined with a pH_stat test. Four types of release behaviors were identified which are characteristic for different elements: (1) release curves that were almost linear with ANC consumption (Ca, Zn, and Cd); (2) release that was significantly faster than ANC (Na, K, and Cl); (3) curves that featured a strong increase with ANC consumption, after a transient release, followed by an almost equal decrease (Si and S); and (4) release that is strongly retarded compared with ANC consumption (Cr, Cu, and Pb). In the SSRC system, it the existence of a pH front and a wash-out phenomenon is demonstrated. Combining the results from the SSRC test with the kinetic analysis of the ANC system in the pH_stat test, it was inferred that less than one-third of the ANC measured from a batch pH titration plays a neutralization role in a field situation. The methodologies described may provide a powerful set of tools for systematic evaluation of element release from solid wastes.     

锰氧化物-阳离子交换树脂复合材料的制备及其对水中重金属的吸附性能

采用原位沉淀-空气氧化法将锰氧化物负载于大孔强酸性阳离子交换树脂D001上,制备出一种新型锰氧化物-阳离子交换树脂复合材料Mn-D001,并对该材料吸附水中Pb2+、Cd2+、Cu2+的性能进行了深入研究.TEM、XRD以及XPS的分析结果表明,负载的锰氧化物以MnO2的形态存在.基于单一金属离子静态吸附的一元体系实验表明,Mn-D001比D001对Pb2+、Cd2+、Cu2+具有更高的吸附选择性,在高浓度竞争离子Ca2+、Mg2+、Na+共存的情况下,仍能保持较高的重金属去除率;Mn-D001对Pb2+、Cd2+、Cu2+的吸附行为符合准一级动力学模型(R2>0.99)和Langmuir吸附等温线模型(R2>0.99).在温度为303 K时,Mn-D001对3种重金属的饱和吸附容量可分别达到476.19 mg.g-1、243.90 mg.g-1及196.08 mg.g-1,优于原有树脂D001.基于复合重金属离子竞争吸附的二元、三元体系的实验表明,Mn-D001对3种重金属的吸附能力顺序为Pb2+>Cu2+>Cd2+,吸附能力由原有树脂D001以及负载的锰氧化物的性质共同决定.     

低品位硅藻土吸附重金属的研究

硅藻土是一种生物硅质沉积岩,具有较大的比表面积,在工业上常用作吸附材料。但低品位硅藻土不利于直接加工利用,在矿产开发中常被忽视或丢弃。为更好地开发和利用低品位硅藻土,采用静态吸附实验研究了低品位硅藻土吸附四种重金属离子（Pb2＋、Zn2＋、Cu2＋、Cd2＋）的动力学规律,用伪一阶、伪二阶模型及粒内扩散模型（Weber和Morris模型）对其吸附过程进行拟合,结果表明,硅藻土对四种重金属离子的吸附均符合伪二阶动力学模型。同时,实验也研究了硅藻土吸附Pb2＋、Zn2＋、Cu2＋、Cd2＋的热力学,并分别用Langmuir、Freundlich和Dubinin-Radushkevich（D-R）方程进行拟合。结果表明,Freundlich和D-R方程都能很好地描述硅藻土对Pb2＋、Zn2＋、Cu2＋、Cd2＋的吸附热力学。并且硅藻土对这四种重金属离子的吸附均为吸热反应。     

Hydrothermal treatment of MSWI fly ash for simultaneous dioxins decomposition and heavy metal stabilization

Researches on the hydrothermal treatment of municipal solid waste incineration (MSWI) fly ash were conducted to eliminate dioxins and stabilize heavy metals. In order to enhance decomposing polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) during hydrothermal process, a strong reductant carbohydrazide (CHZ) is introduced. A hydrothermal reactor was set up by mixing raw MSWI fly ash or the pre-treated fly ash with water and then heated to a pre-set temperature; CHZ was spiked into solution according to specially defined dosage. Experimental results showed that under the temperatures of 518 K and 533 K, the decomposition rates of PCDDs/PCDFs were over 80% and 90%, respectively, by total concentration. However, their toxic equivalent (TEQ) decreased only slightly or even increased due to the rising in concentration of congeners 2, 3, 7, 8-TCDD/TCDF, which might be resulted from the highly chlorinated congeners losing their chlorine atoms and being degraded during the hydrothermal process. Better results of TEQ reduction were also obtained under the higher tested temperature of 533 K and reactor with addition of 0.1%wt CHZ was corresponded to the best results. Good stabilization of heavy metals was also obtained in the same hydrothermal process especially when ferrous sulphate was added as auxiliary agent.     

Effect of seawater salinity on the synthesis of zeolite from coal fly ash

A novel method for the synthesis of zeolite was developed in this paper. The synthesis was carried out by hydrothermal activation after alkali fusion and coal fly ash （CFA） was used as raw material with seawater of different salinities. Seawater salinity was varied from 32 to 88 for zeolite crystallization during the hydrothermal process. The results show that seawater salinity plays an important role in zeolite synthesis with CFA during hydrothermal treatment. The products were a mixture of NaX zeolite and hydroxysodalite; seawater salinity more strongly affected the crystallization than the type and chemical composition of the zeolites. The yield of CFA transformed into zeolite gradually rose with the increase in salinity, reaching a transformation rate of 48%--62% as the salinity increased from 32 to 88, respectively. The proposed method allows for the efficient disposal of by-products; therefore, the application of seawater in zeolite synthesis presents promising economic and ecological benefits.     

Effects of organic matter on the specific adsorption of heavy metals by soil

The adsorption of heavy metals on soil from the Neihu Landfill Site in Taipei City was investigated in order to assess the groundwater pollution problems. The effects of soil organic matter and the behaviors of organic complexing ligands like EDTA and humic acid to the overall adsorption process were studied and discussed. For explaining the results, the pH value of soil system and the properties of the soil/aqueous interface were chosen as two significant and interacted factors for discussion. The concept of the specific adsorption mechanism was also demonstrated and discussed. The results showed that the complexing ligands existing in soil liquid phase have more influences than natural organic matter does. The competitive sequences of different organic matter contents indicated that organic functional sites preferentially bind with Cu and Cd. The presence of EDTA and humic acid which formed ligandlike complexes will reduce Cd adsorption efficiency. These effects will induce mobility and the fate of heavy metals in soils, such as bioavailability.     

磁性海泡石吸附水中重金属离子的特性及机理

以化学共沉淀法制备磁性海泡石,通过设置一个外加磁场实现对其的分离回收.主要研究了磁性海泡石吸附水中重金属离子的特性,并结合XRD、FT-IR分析结果探讨了吸附机理,结果表明,磁性海泡石对重金属阳离子的吸附效果优于阴离子;初始pH对磁性海泡石吸附重金属离子的影响不仅取决于磁性海泡石表面的电荷性质,而且与重金属离子的水解能力有关;在吸附过程中,磁性海泡石的物相结构没有发生明显改变,吸附机理表现为离子交换和配合吸附作用.     

PCDD/DFs and coplanar PCBs in fly ash samples from various types of incinerators in Taiwan

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/DFs) and coplanar polychlorinated biphenyls (Co‐PCBs) were determined in fly ash samples from municipal solid waste (MSW), medical waste (MW), and electricity power plant incinerators in Taiwan. The average concentrations of PCDD/DFs and Co‐PCBs are 7.02 ng‐TEQ/g and 1.06 ng‐TEQ/g, respectively. The contributions to total TEQ are 24% from PCDDs, 64% from PCDFs, and 12% from Co‐PCBs, indicating that PCDFs generate the highest environmental impact and MSW and MW incinerators are potential Co‐PCBs contaminating sources. The levels of PCDD/DFs and Co‐PCBs found in ash samples increase from petroleum‐fired, coal‐fired, large municipal solid waste, small medical waste, to small municipal solid waste incinerators, and are generally lower than those from incinerators built earlier. All fly ash samples analyzed in this study were considered hazardous materials. More research is suggested to establish the relationship between the amounts of PCDD/DFs and Co‐PCBs in fly ash and in flue gas.     

溶解性有机物对土壤中重金属环境行为的影响

为揭示在溶解性有机物（DOM）作用下土壤中重金属的吸附和迁移规律并确定迁移数学模型,通过不同条件下的等温吸附实验和土柱淋滤实验,研究了溶解性有机物对重金属Cu,Cd,Pb,Zn在褐土中吸附和迁移行为的影响。结果表明DOM对Cu和Cd在土壤中的吸附促进作用较明显,对Pb有微弱的促进作用,对Zn的吸附影响不明显;随着pH的改变,25℃下Cu在土壤中的吸附高于15℃和35℃条件下。DOM质量浓度越高,Cd、Zn溶出的促进效果越明显,Cu、Pb则恰好相反。DOM对土壤中Cd、Zn的垂直迁移起着促进作用,而对Cu、Pb迁移起着一定的抑制作用;DOM对土壤重金属的平均迁移量随时间的延长而减少。此迁移模型能够定量计算并预测重金属质量浓度的时空分布。     

Accumulation and translocation of heavy metals in soil and plants from fly ash contaminated area

The present investigation deals with the accumulation of heavy metals in fields contaminated with fly ash from a thermal power plant and subsequent uptake in different parts of naturally grown plants. Results revealed that in the contaminated site, the mean level of all the metals (Cd, Zn, Cr, Pb, Cu, Ni, Mn and Fe) in soil and different parts (root and shoots) of plant species were found to be significantly (p<0.01) higher than the uncontaminated site. The enrichment factor (EF) of these metals in contaminated soil was found to be in the sequence of Cd (2.33) > Fe (1.88) > Ni (1.58) > Pb (1.42) > Zn (1.31) > Mn (1.27) > Cr (1.11) > Cu (1.10). Whereas, enrichment factor of metals in root and shoot parts, were found to be in the order of Cd (7.56) > Fe (4.75) > Zn (2.79) > Ni (2.22) > Cu (1.69) > Mn (1.53) > Pb (1.31) > Cr (1.02) and Cd (6.06) approximately equal Fe (6.06) > Zn (2.65) > Ni (2.57) > Mn (2.19) > Cu (1.58) > Pb (1.37) > Cr (1.01) respectively. In contaminated site, translocation factor (TF) of metals from root to shoot was found to be in the order of Mn (1.38) > Fe (1.27) > Pb (1.03) > Ni (0.94) > Zn (0.85) > Cd (0.82) > Cr (0.73) and that of the metals Cd with Cr, Cu, Mn, Fe; Cr with Pb, Mn, Fe and Pb with Fe were found to be significantly correlated. The present findings provide us a clue for the selection of plant species, which show natural resistance against toxic metals and are efficient metal accumulators.     

重金属污染物的免疫学检测技术研究进展

重金属的免疫学检测是一种新型的重金属检测方法，与传统检测方法相比，具有省时、省力、费用低廉、便于携带、易于操作等优点，能用于重金属污染物的现场快速检测和常规检测，这对于重金属污染地区的补救和恢复工作具有很大的意义，因而发展和普及应用潜力很大。国外学者通过选择或合成双功能鳌合剂鳌合重金属离子并与载体蛋白偶联制备出完全抗原，进一步制备出金属特异性单抗。目前应用免疫学检测方法检测环境中的重金属离子还处于实验室的试验阶段，初步实验结果表明KinExA免疫检测法具有用作重金属免疫检测传感器的能力，并且越来越多的重金属检测模型被开发出来。金属特异性抗体一抗原的结合属性的初步研究表明，影响抗体对抗原识别的主要因素有：金属离子的半径、电子和形态上的并协性；鳌合剂的结构；金属离子一鳌合剂复合物三维结构和价态结构；抗体中的某些氨基酸残基能与抗原中金属离子直接配位以及与抗原中的鳌合剂部分发生相互作用（疏水作用、氢键作用等）。     

利用非活体生物质去除废水中重金属的研究

为了解非活体牛物质去除废水中重金属的效果，选择了玉米芯、水稻谷壳、花生壳、松树树皮和茶叶等5种非活体生物质，州室内模拟方法比较研究了它们对重金属的吸附能力。结果表明，生物质对重金属的吸附是一个快速反应，可在20-30min内达到平衡。pH值对牛物质吸附阳离子型重金属有很大的影响，吸附量随pH值上升而增加，pH值在4．5以上时可达到较高水平。5种生物质对重金属都有较高吸附能力，它们吸附重金属的能力依次为：花生壳〉松树树皮〉玉米芯〉水稻谷壳〉茶叶。生物质去除废水中重金属的效果一般为：Cu、Pb〉Cd〉Zn。用碱、柠檬酸和磷酸对生物质进行改性处理可显著增强其对重金属的去除能力。生物质是一种廉价、有效的吸附剂，可替代商品吸附剂用于废水中重金属的去除，主要重金属的移除率在85％以上。