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垃圾焚烧产生二噁英。

Dioxin formation from waste incineration.

作者信息

Shibamoto Takayuki, Yasuhara Akio, Katami Takeo

机构信息

Department of Environmental Toxicology, University of California, Davis, CA 95616, USA.

出版信息

Rev Environ Contam Toxicol. 2007;190:1-41. doi: 10.1007/978-0-387-36903-7_1.

Abstract

There has been great concern about dioxins-polychlorinated dibenzo dioxins (PCDDs), polychlorinated dibenzo furans (PCDFs), and polychlorinated biphenyls (PCBs)-causing contamination in the environment because the adverse effects of these chemicals on human health have been known for many years. Possible dioxin-contamination has received much attention recently not only by environmental scientists but also by the public, because dioxins are known to be formed during the combustion of industrial and domestic wastes and to escape into the environment via exhaust gases from incinerators. Consequently, there is a pressing need to investigate the formation mechanisms or reaction pathways of these chlorinated chemicals to be able to devise ways to reduce their environmental contamination. A well-controlled small-scale incinerator was used for the experiments in the core references of this review. These articles report the investigation of dioxin formation from the combustion of various waste-simulated samples, including different kinds of paper, various kinds of wood, fallen leaves, food samples, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polyvinylidene chloride, polyethylene tetraphthalate (PET), and various kinds of plastic products. These samples were also incinerated with inorganic chlorides (NaCl, KCl, CuCI2, MgCl2, MnCl2, FeCl2, CoCl2, fly ash, and seawater) or organic chlorides (PVC, chlordane, and pentachlorophenol) to investigate the role of chlorine content and/or the presence of different metals in dioxin formation. Some samples, such as newspapers, were burned after they were impregnated with NaCl or PVC, as well as being cocombusted with chlorides. The roles of incineration conditions, including chamber temperatures, O2 concentrations, and CO concentrations, in dioxin formation were also investigated. Dioxins (PCDDs, PCDFs, and coplanar-PCBs) formed in the exhaust gases from a controlled small-scale incinerator, where experimental waste samples were burned, were analyzed by gas chromatography/mass spectrometry. Formation of total PCDFs was much higher than that of PCDDs in all samples. The total PCDFs comprised 70%-90% of the total dioxin formed. The amount of total PCDFs formed ranged from 0.78 ng/g (newspaper) to 8,490ng/g (PVC burned in high CO concentration). The amount of total PCDDs formed ranged from 0.02ng/g (newspaper) to 430ng/g (PVC). Coplanar PCBs were found at the lowest level of the dioxins formed. Their formation levels ranged from 0ng/g (newspaper) to 77.6ng/g (PVC). It is obvious that the samples with either inorganic or organic chlorides produced much more dioxins than the sample without chlorides when incinerated under similar conditions. It is not clear how inorganic and organic chloride contribute differently to dioxin formation. Among the metals examined, copper seems to have higher activity toward dioxin formation than other metals. It acted not only as a catalyst but also as a transmitter of heterogeneous chlorine. The toxicity equivalence quantity (TEQ) values generally correlated with the amount of chlorine content in the samples and the amount of dioxin formed in exhaust gases from an incinerator. When the same sample was incinerated at different temperatures, however, the sample burned at low temperature yielded a higher TEQ value than did the sample burned at high temperature. The samples that did not contain chlorine or were not combusted with chlorides exhibited low TEQ values. In contrast, samples with high chlorine content, such as PVC (51.3%), gave high TEQ values. Combustion temperatures may play an important role in dioxin formation in exhaust gases from the incineration of waste materials. However, no significant relationship between dioxin formation and chamber temperatures was reported in the core articles. However, It is obvious that dioxin formation occurred at temperatures above 450'C and was reduced significantly at temperatures above 850 degrees C. The reaction occurring in an incinerator is extremely complex, and there are many factors in addition to combustion temperature influencing dioxin formation. Even though it is possible to hypothesize reasonable formation mechanisms of dioxins produced in exhaust gases according to the results obtained from experiments in classical chemistry, the reactions involved in an incinerator are extremely complex and heterogeneous. More detailed investigation of the many individual factors influencing dioxin formation is needed to find ways to reduce their formation in individual and municipal incinerators.

摘要

二噁英(多氯二苯并二噁英(PCDDs)、多氯二苯并呋喃(PCDFs)和多氯联苯(PCBs))对环境造成污染已引发了广泛关注,因为这些化学物质对人类健康的不利影响已为人所知多年。近期,二噁英可能造成的污染不仅受到环境科学家的高度关注,也引起了公众的注意,因为二噁英已知是在工业和生活垃圾燃烧过程中形成,并通过焚烧炉的废气排放到环境中。因此,迫切需要研究这些含氯化学物质的形成机制或反应途径,以便能够设计出减少其环境污染的方法。本综述的核心参考文献中使用了一个控制良好的小型焚烧炉进行实验。这些文章报道了对各种模拟废物样品燃烧过程中二噁英形成的研究,这些样品包括不同种类的纸张、各种木材、落叶、食品样品、聚乙烯(PE)、聚苯乙烯(PS)、聚氯乙烯(PVC)、聚偏二氯乙烯、聚对苯二甲酸乙二酯(PET)以及各种塑料制品。这些样品还与无机氯化物(NaCl、KCl、CuCI2、MgCl2、MnCl2、FeCl2、CoCl2、飞灰和海水)或有机氯化物(PVC、氯丹和五氯苯酚)一起焚烧,以研究氯含量和/或不同金属的存在在二噁英形成中的作用。一些样品,如报纸,在浸渍NaCl或PVC后以及与氯化物共燃烧后进行燃烧。还研究了焚烧条件,包括炉膛温度、O2浓度和CO浓度,在二噁英形成中的作用。通过气相色谱/质谱法分析了在受控小型焚烧炉中燃烧实验废物样品时废气中形成的二噁英(PCDDs、PCDFs和共平面PCBs)。在所有样品中,PCDFs的总生成量远高于PCDDs。PCDFs总量占二噁英总生成量的70%-90%。PCDFs的总生成量范围为0.78 ng/g(报纸)至8490 ng/g(在高CO浓度下燃烧的PVC)。PCDDs的总生成量范围为0.02 ng/g(报纸)至430 ng/g(PVC)。共平面PCBs在形成的二噁英中含量最低。其生成水平范围为0 ng/g(报纸)至77.6 ng/g(PVC)。显然,在类似条件下焚烧时,含有无机或有机氯化物的样品比不含氯化物的样品产生的二噁英要多得多。目前尚不清楚无机和有机氯化物对二噁英形成的贡献有何不同。在所研究的金属中,铜似乎比其他金属对二噁英形成的活性更高。它不仅起到催化剂的作用,还作为异相氯的传递体。毒性当量(TEQ)值通常与样品中的氯含量以及焚烧炉废气中形成的二噁英量相关。然而,当相同样品在不同温度下焚烧时,低温燃烧的样品产生的TEQ值高于高温燃烧的样品。不含氯或未与氯化物一起燃烧的样品TEQ值较低。相比之下,氯含量高的样品,如PVC(51.3%),TEQ值较高。燃烧温度可能在废物焚烧废气中二噁英的形成中起重要作用。然而,核心文章中未报道二噁英形成与炉膛温度之间存在显著关系。然而,很明显二噁英的形成发生在450℃以上的温度,而在850℃以上的温度时显著减少。焚烧炉中发生的反应极其复杂,除了燃烧温度外,还有许多因素影响二噁英的形成。尽管根据经典化学实验结果有可能推测出废气中产生的二噁英的合理形成机制,但焚烧炉中涉及的反应极其复杂且具有异相性。需要对影响二噁英形成的许多个体因素进行更详细的研究,以找到减少其在个体和城市焚烧炉中形成的方法。

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