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.     

城市垃圾焚烧飞灰中重金属的形态及酸浸出性研究

研究了城市垃圾焚烧飞灰中重金属形态在不同粒径上的分布,以及HNO3对飞灰中重金属的浸出性.结果表明:飞灰中重金属主要以残渣态存在,可交换离子态含量很少;易挥发性的重金属在较大粒径上有较高分布,亲石性重金属Cr和Ni的分布与粒径的相关性不大,在各粒径上的分布较均匀;飞灰中以碳酸盐结合态存在的重金属对酸不稳定,易被HNO3浸出,而残渣态部分对酸较稳定,不易被HNO3浸出.     

Fates and partitioning of heavy metals in municipal solid waste incineration process

The fate and partitioning of heavy metals (including Hg, Cd, Pb, Zn, As, Cr, Ni, and Cu) from MSW incinerators located in Taiwan were determined. Results of stack sampling indicate that most Hg and As (more than 80%) exists in the gas phase while other metals partition differently among bottom ash, fly ash, and flue gases. Removal efficiencies of existing air pollution control devices for Hg and As are lower (about 70%) than other metals. Bottom ash contains higher concentration of Cd compared with European incinerators. In addition, strong enrichment of Cd on fly ash particles is observed.     

外源铅铜镉在长三角和珠三角农业土壤中的转化

选择了我国经济发达地区的长江三角洲和珠江三角洲10个代表性农业土壤，采用室内培养和化学分级方法研究了加入外源铅、铜、镉在土壤中的动态变化及转化趋势，探讨了碳酸钙、粉煤灰、猪粪和钢渣等土壤改良剂对土壤重金属形态的影响。结果表明，随着土壤重金属负荷的提高，土壤中交换态重金属的比例增大，残余态比例下降，有效性提高，对环境威胁增大。当重金属加入最较低时，重金属优先向氧化物结合态、有机质结合态转化；而当加入最较高时，向交换态和碳酸盐结合态转化的比例明皿增加。pH和土壤组分对重金属在土壤中的转化有显著的影响，土壤pH下降可使交换态Cd、Cu、Pb的比例递增。加入碳酸钙、粉煤灰、猪粪和钢渣等改良剂可显著地降低土壤中交换态重金属比例，增加其它形态的重金属比例。     

Leaching Characteristics of Lead and Cadmium From Waste-To-Energy Residues in Sea Water

Laboratory studies were conducted to determine leaching characteristics of waste-to-energy (WTE) residues in sea water to provide initial evaluation on the potential impact of WTE residues on the marine environment. Both loose and stabilized WTE residues were investigated for the leachability of lead (Pb) and cadmium (Cd) in sea water. Results of the study showed that loose WTE fly ash was very reactive in sea water; release of Pb and Cd occurred immediately (<0.5 hr) after the ash came in contact with sea water. Stabilization (treated with Portland cement and other additives), however, significantly reduced leaching of Cd and Pb. While ocean disposal of untreated WTE residues would not be advisable, utilization of stabilized WTE residues for beneficial uses should be investigated.     

Characteristics of the stabilized/solidified municipal solid wastes incineration fly ash and the leaching behavior of Cr and Pb

Fly ash is a hazardous byproduct of municipal solid wastes incineration (MSWI). An alkali activated blast furnace slag-based cementitious material was used to stabilize/solidify the fly ash at experimental level. The characteristics of the stabilized/solidified fly ash, including metal leachability, mineralogical characteristics and the distributions of metals in matrices, were tested by toxic characteristic leaching procedure (TCLP), X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectrometer (SEM-EDS) respectively. Continuous acid extraction was utilized to extract metal ions and characterize their leaching behavior. The stabilization/solidification procedure for MSWI fly ash demonstrates a strong fixing capacity for the metals by the formation of C-S-H phase, hydrated calcium aluminosilicate and ettringite. The stabilized/solidified fly ash shows a dense and homogeneous microstructure. Cr is mainly solidified in hydrated calcium aluminosilicate, C-S-H and ettringite phase through physical encapsulation, precipitation, adsorption or substitution mechanisms, and Pb is mainly solidified in C-S-H phase and absorbed in the Si-O structure.     

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.     

Experiences of Coal Ash Artificial Reefs in Taiwan

A feasibility study for using fly-ash from Taiwan coal-fired power stations for artificial reef production was started in 1983. Various mixtures of fly ash stabilized with lime, cement, or industrial wastes and formed into blocks were tested in the laboratory. the results showed that the development of compressive strength of those blocks immersed in the sea water was much better than those exposed in the air. Heavy metal (Cd, Cr, Cu, Ni, Pb, Zn) content of the blocks has been monitored routinely to determine the leaching rates. the result indicates that solidification of fly-ash could indeed immobilize heavy metals better than the original fly ash. From March 1984 to February 1987, 3,682 coal ash stabilized blocks with total weight of 300 tons were designed, fabricated and installed at both Hsin-ta, south western coast, and Kuei-hou, northern coast of Taiwan, for field trials. After four years' underwater observations on 100 cubic blocks at Wan-Li, northern Taiwan, it was shown that the physical integrity of the ash reef blocks had been maintained. the compressive strength and durability was better than the concrete artificial reefs nearby. the ash reefs could also attract fishes and the colonization by benthic organisms was similar to that on concrete reefs. Eighty-eight species of fishes were observed, of which 27 were commercially important, comprising more than 80% of the total biomass. These results demonstrate a potential use for stabilized coal ash as artificial reefs to replace traditionally used concrete reefs to protect and enhance the coastal fishery resources in Taiwan in the future.     

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.     

利用废弃物煅烧水泥时重金属Pb、Cd的逸放污染

利用废弃物作为代替原料煅烧水泥已广泛应用于水泥生产,但其带来的环境污染问题不容忽视。以利用废弃物生产水泥的厂家为研究对象,采用原子吸收分光光度法检测所采集样品中重金属Pb、Cd的含量,对水泥生产过程中重金属Pb、Cd的逸放及其对周围土壤的污染进行研究。研究结果表明:利用废弃物煅烧水泥的过程中,重金属Pb、Cd的逸放率很高,其中立窑的Pb、Cd逸放率高达84%～90%,湿法回转窑的Pb、Cd逸放率达到63%～74%;在水泥厂上下风向500m、1000m和2000m处采集土壤样品,工厂周围的土壤均已受到不同程度的重金属污染,位于工厂下风向的土壤受到的污染更为严重,距离工厂500m处土壤中重金属Pb、Cd的含量均超过了国家标准的最大限量;对几家工厂员工的头发进行随机取样,头发样品中Pb含量均超过正常限量。     

Coal fly ash and straw immobilize Cu,Cd and Zn from mining wasteland

Soil heavy metal contamination is a major health issue. Chemical immobilization of toxic metals is a promising technique to solve this issue. In this study, soil was sampled from a copper mining-polluted area in eastern China. Coal fly ash and straw were applied to soil samples at 5 % w/w ratio and 2 % w/w ratio, and incubated for 6 weeks. The CaCl₂-extractable Cu, Cd and Zn, phytoavailability and soil microbial activity were measured. The results showed that coal fly ash, straw and the mixture of coal fly ash and straw decreased CaCl₂-extractable metals. Coal fly ash or the mixture of the two amendments are therefore efficient metal stabilizers.     

镍钴采选行业废石和尾矿中重金属淋溶释放规律研究

镍钴采选废石和尾矿中重金属的溶出释放规律对矿区的重金属污染防治具有重要意义。但目前,国内还没有对镍钴行业采选产生的尾矿和废石中重金属的溶出规律开展研究。本文以镍钴采选企业的尾矿和废石作为样本,开展了毒性浸出实验。研究了不同pH值、离子强度、温度等实验条件对重金属溶出的影响,探讨了镍钴采选过程中所产生的尾矿和废石中重金属的溶出特性和释放规律。实验结果表明,尾矿样品中Ni的浸出浓度为42.28 mg·L^-1,是最大允许排放浓度的8.86倍,为具有浸出毒性特征的危险废物;废石样品中重金属Ni和Cu的溶出浓度分别为4.72 mg·L^-1和26.2 mg·L^-1,超过最大允许排放浓度,属于第Ⅱ类一般工业固体废物。pH对样品中Ni、Cr、Pb、Co和As的溶出量影响较大,其中尾矿中Ni和Cu在pH较低的条件下,可达到44.28 mg·L^-1和53 mg·L^-1,远高于最大允许排放浓度,而Hg、Cd和Cu的溶出量随pH值的变化不大。除As以外,样品中大多数重金属的溶出质量浓度在酸性条件下比在中性条件下高,这表明在酸性环境条件下,这些重金属对周围生态环境的潜在风险更大。离子强度的变化对Cd和Co的溶出量的变化并不明显,而当离子强度变化时,Ni、Cr、Pb、Hg、Cu和As的溶出量可能达到最大,使周围环境的潜在生态风险增大。当温度达到35~40℃时,部分重金属如Co、Pb、Cd 等,溶出量将达到最大;当温度低于25℃时,除 Ni 以外,大部分重金属溶出量很低。而温度变化对重金属Cu、As、Cr和Hg的溶出量的影响不明显,波动范围较小,对周围生态环境产生的潜在生态风险较小。     

燃煤烟气脱硫副产物的重金属环境行为

通过理化分析、盆栽生物试验及土壤淋溶试验，探讨了脱硫副产物的重金属农业环境行为。结果表明：燃煤烟气脱硫副产物中的总Pb、Cd、Cr、As、Se、Ni、Cu等指标，基本上都低于国标最高容许量和土壤环境质量二级标准，符合国家控制标准，但普遍高于土壤自然背景值含量。8～10g／kg土的供试物量处理，花生、萝卜、甘蔗和水稻的可食部分重金属均无超常累积现象，未导致农产品重金属的富集残留污染，不影响农产品安全品质。在表土层供试物量达到40g／kg条件下，土壤淋溶试验结果表明，施脱硫副产物未导致土壤淋滤液重金属污染，不可能通过降雨淋溶过程，渗透过1m左右的土层而污染地下水源。     

Stability of a Coal Waste Artificial Reef

The feasibility of using U.K. coal-fired power station waste materials for artificial reef production is being examined. in June, 1989, an experimental artificial reef was constructed in Poole Bay, off the central south coast of the U.K., using three different mixtures of pulverised fuel ash (PFA), flue gas desulphurisation (FGD) gypsum and slurry, stabilized with cement and formed into blocks. Fifty tonnes of 40 × 20 × 20 cm blocks were formed into eight conical reef units replicating three different PFA/gypsum mixtures and one concrete control. the reef structure is 10m below chart datum on a flat sandy sea-bed.

Combustion of coal concentrates the heavy metal content in the resultant ash. the purpose of stabilization of the ash as blocks is twofold: to immobilize heavy metals (or other components) and to provide hard substratum for the attachment of organisms. to examine the effectiveness of this stabilization and hence the environmental compatibility of the block materials, heavy metal (Cd, Cr, Cu, Pb, Mn, Ni, Zn) content of the blocks has been monitored routinely over two years, to determine leaching rates. Sectional profiles indicate partial replacement of calcium content by magnesium. Associated with this there has also been some redistribution of heavy metals. Only in the case of cadmium has there been a detectable loss from the surface of blocks. Chromium and manganese concentrations appear to have increased. the metal content of the reef epibiota (including ascidians, Ascidia mentula; hydroids, Halecium spp.; bryozoans, Bugula spp. and red algae) growing on the ash blocks has been compared to that of epibiota attached to the concrete controls and surrounding sea-bed. to date no evidence of excess bioaccumulation of metals has been detected.

The physical integrity of the ash reef blocks has been maintained. There is evidence that the blocks are increasing in compressive strength.

An indication of the fishery enhancement potential of the experimental structure is given by the presence of eight commercially fished species (crustaceans and molluscs) including lobsters (Homarus gammarus).     

Stability of a Coal Waste Artificial Reef

The feasibility of using U.K. coal-fired power station waste materials for artificial reef production is being examined. in June, 1989, an experimental artificial reef was constructed in Poole Bay, off the central south coast of the U.K., using three different mixtures of pulverised fuel ash (PFA), flue gas desulphurisation (FGD) gypsum and slurry, stabilized with cement and formed into blocks. Fifty tonnes of 40 × 20 × 20 cm blocks were formed into eight conical reef units replicating three different PFA/gypsum mixtures and one concrete control. the reef structure is 10m below chart datum on a flat sandy sea-bed.

Combustion of coal concentrates the heavy metal content in the resultant ash. the purpose of stabilization of the ash as blocks is twofold: to immobilize heavy metals (or other components) and to provide hard substratum for the attachment of organisms. to examine the effectiveness of this stabilization and hence the environmental compatibility of the block materials, heavy metal (Cd, Cr, Cu, Pb, Mn, Ni, Zn) content of the blocks has been monitored routinely over two years, to determine leaching rates. Sectional profiles indicate partial replacement of calcium content by magnesium. Associated with this there has also been some redistribution of heavy metals. Only in the case of cadmium has there been a detectable loss from the surface of blocks. Chromium and manganese concentrations appear to have increased. the metal content of the reef epibiota (including ascidians, Ascidia mentula; hydroids, Halecium spp.; bryozoans, Bugula spp. and red algae) growing on the ash blocks has been compared to that of epibiota attached to the concrete controls and surrounding sea-bed. to date no evidence of excess bioaccumulation of metals has been detected.

The physical integrity of the ash reef blocks has been maintained. There is evidence that the blocks are increasing in compressive strength.

An indication of the fishery enhancement potential of the experimental structure is given by the presence of eight commercially fished species (crustaceans and molluscs) including lobsters (Homarus gammarus).     

Characterization of boron tolerant bacteria isolated from a fly ash dumping site for bacterial boron remediation

Boron is an essential micronutrient for plants, but can above certain concentrations be toxic to living organisms. A major environmental concern is the removal of boron from contaminated water and fly ash. For this purpose, the samples were collected from a fly ash dumping site, Nagasaki prefecture, Japan. The chemical characteristics and heavy metal concentration of the samples were performed by X-ray fluorescent analysis and leaching test. For bacterial analysis, samples were collected in sterile plastic sheets and isolation was carried out by serial dilution method. The boron tolerant isolates that showed values of maximum inhibitory concentration toward boron ranging from 100 to 260 mM level were screened. Based on 16S rRNA sequencing and phylogenetic analysis, the isolates were most closely related to the genera Bacillus, Lysinibacillus, Microbacterium and Ralstonia. The boron tolerance of these strains was also associated with resistant to several heavy metals, such as As (III), Cr (VI), Cd, Cu, Pb, Ni, Se (III) and Zn. Indeed, these strains were arsenic oxidizing bacteria confirmed by silver nitrate test. These strains exhibited their salt resistances ranging from 4 to 15 % were determined in Trypticase soy agar medium. The boron tolerant strains were capable of removing 0.1–2.0 and 2.7–3.7 mg l^?1 boron from the medium and fly ash at 168 h. Thus, we have successfully identified the boron tolerant and removal bacteria from a fly ash dumping site for boron remediation.     

燃煤电厂排放颗粒物中重金属形态的研究

本文分析用模拟酸雨浸提和Ｔｅｓｓｉｅｒ形态分离法，对燃煤电厂排放颗粒物中重金属形态进行了研究。结果表明，痕量金属绝大部分以稳定态存在，微米级飞灰中有较大活性的形态高于灰渣，煤燃烧高温条件使颗粒物中活性较大的形态含量减小。     

三峡库区主要粮食作物和土壤中重金属的相关性及富积特征分析

采用野外采样和室内分析,试验结果表明三峡库区土壤中重金属Cu、Zn、Pb、Cd、Fe、Cr的变异系数小于50%,重金属的含量比较稳定。稻谷（Oryza sativa）中Cu、Zn、Pb、Cd、Fe、Mn、Cr,玉米（Zea mays）中Pb、Cd、Fe、Mn、Cr和小麦（Triticum aestivum）中Cu、Pb、Cd、Fe、Mn、Cr的变异系数大于50%。土壤、稻谷、玉米、小麦中大部分重金属呈偏态分布。土壤中重金属间均为正相关,且极显著正相关性明显。稻谷、玉米、小麦中重金属间有正相关,也有负相关,但正相关明显多于负相关;稻谷、玉米、小麦中Mn同其它重金属间均有显著正相关性,协同作用明显。稻谷、玉米、小麦中Pb、Cd、Cr的样本超标率较大,污染明显,并且稻谷中Cd与土壤中Cd有直线关系。     

Assessment of solid waste and dumpsite leachate and topsoil

Dumpsite leachate contains different hazardous substances, some of which threaten the environment. In this study, municipal solid waste, dumpsite leachate and topsoil from seven different dumpsites in Lagos and Ibadan, Nigeria were analysed using standard methods. The parameters analysed in the composite leachate samples collected are pH, solids, alkalinity, chloride, nitrate, sulfate, phosphate, biochemical oxygen demand, chemical oxygen demand turbidity, heavy metals (e.g. Zn, Pb, Co, Ni, Cd) and some persistent organic pollutants (e.g. polyaromatic hydrocarbons [PAHs] and polychlorinated biphenyls [PCBs]). Total organic carbon, heavy metals (e.g. Zn, Pb, Co, Ni, Cd) and organic pollutants (e.g. PAHs, PCBs) were analysed in the dumpsite topsoil and the control samples. The samples for heavy metal determination were digested using concentrated nitric acid and the digestate was analysed using atomic absorption spectrometry, whereas organic pollutants were extracted using cold extraction and quantified by gas chromatography-mass spectrometry (GC-MS). The study revealed that dumpsites in Ibadan have ～90% domestic and 10% industrial waste, whereas the figures for Lagos are 80% and 20%, respectively. In the leachate samples, concentrations of PAHs and PCBs ranged from 0.85 to 1.47 mg/L and 0.01 to 0.08 mg/L, respectively; the values were 0.94–2.79 mg/kg and 10.0–412 μg/kg in the topsoil. If not properly managed, dumpsite leachate can seep into groundwater and surface water via run-off, and can have adverse effects on human health and the entire ecosystem.     

A new method to inertize incinerator toxic fly ash with silica from rice husk ash

Fly ash from municipal solid waste incineration is a toxic waste due to the presence of toxic heavy metals. Here, a new method for metal stabilization based on the use of silica gel extracted from rice husk ash is presented. This method is sustainable because of the use of only waste materials to produce a final inert product, and because the inertization procedure occurs at room temperature. The estimated maximum Pb adsorption capacity of extracted silica, of about 36 mg/g, is found to be far greater than the adsorption capacity of other known absorbers used for municipal solid waste incineration fly ash.