火化过程中二噁英类污染物减排技术研究

为减少火化过程中二噁英类污染物的排放,研究了"热交换器 布袋除尘器 活性炭纤维毡"三级组合对火化遗体烟气中二噁英类污染物的去除效果.利用急冷技术将二次燃烧室排出的火化烟气温度降到90～130℃.实验表明,布袋除尘器去除火化烟气中二噁英类污染物的效率为57.4%;布袋除尘器分别与厚度为5、15 mm的活性炭纤维毡组合去除火化烟气中二噁英类污染物的效率分别为64.0%和89.2%.     

垃圾焚烧发电厂二噁英控制方案的技术经济分析

严格控制二噁英类污染物的排放,是顺利推进垃圾焚烧发电厂建设及运行的难点和重点.对民众而言,如何最大程度地降低二噁英的排放是其关注的内容;对企业而言,如何经济有效地控制二噁英的排放是其关注的主要任务.以活性炭喷射吸附二噁英和选择性催化分解二噁英(简称催化分解方案)为主导结合常规尾气处理技术是垃圾焚烧发电厂控制二噁英排放的2种主要的末端方案.并以每天700t焚烧能力的垃圾焚烧发电厂为例,综合比较了上述2种方案,包括技术特征和处理效果;计算2种方案的设备成本、运行成本、等值年成本对垃圾焚烧发电厂运行的经济影响.指出催化分解方案的监督运行成本较低、总体减排效果更显著,因此在中国经济发达地区和环境质量要求较高的区域可试行催化分解方案.     

小型焚烧设施烟气中二噁英类的排放和控制

对中国典型的小型焚烧设施现状和二噁英类排放进行了初步调查研究,未经处理的小型垃圾焚烧设施烟气中二噁英类毒性当量(TEQ)大于6 ng/m3,小型火化机烟气中二噁英类TEQ大于5 ng/m3.设计并检验了布袋除尘器和活性炭滤布的二噁英类去除效果.仅使用布袋除尘器二噁英类去除率不高,布袋除尘器和活性炭滤布联用可以有效去除飞灰和气相中的二噁英类,去除率达到90%左右,可达到《生活垃圾焚烧污染控制标准》(GB 18485-2001)二噁英类排放标准.     

国内外二噁英检测标准制修订现状与进展

综述了当前国内外一些标准机构和组织制定的二噁英类物质检测与限量标准,并介绍了相关技术在二噁英检测标准中的应用和发展,希望能为广大相关检测人员提供一定的使用参考。     

二噁英受体的配体多样性研究进展

二噁英受体(AHR)是一种依赖于配体激活的转录因子,在细胞增殖与分化、细胞凋亡、癌细胞迁移以及炎症反应等多种生物学过程中具有至关重要的作用。AHR的激活依赖于外界环境中的多种有毒化合物或内源性配体的结合,不同类型配体通过激活AHR的不同信号通路发挥不同的功能。对不同结合位点的AHR配体分子进行归纳、总结,并对几类典型的激动剂和拮抗剂激活AHR的机制及其在不同疾病中的潜在毒理作用进行综述。深入了解AHR的激活机制及其毒理作用将有助于预防和治疗环境污染物所导致的疾病,并为以AHR为靶点的药物开发提供一定的理论指导。     

碳酰肼对烧结过程二噁英生成的抑制作用

研究了碳酰肼对钢铁厂烧结工序产生的二噁英的抑制效果。结果表明,添加了0.01%(质量分数,下同)、0.02%、0.05%、0.10%的碳酰肼之后,二噁英的排放质量浓度降为0.560、0.506、0.270、0.174ng-TEQ/m3,相对于基准值(0.821ng-TEQ/m3)大幅减少。碳酰肼对二噁英的从头合成以及前驱物生成都能起到一定的抑制效果。碳酰肼与Cu2+结合生成稳定的氮化物,削弱Cu2+的催化活性;与HCl反应,减少了生成二噁英的氯源;对FeCl3、CuCl2的催化活性也会产生影响。碳酰肼添加后,对多氯代二苯并呋喃(PCDFs)生成中高氯代二噁英的脱氯行为也有明显的抑制。     

中国二噁英排放清单的国际比较研究

采用年总排放量、向大气年排放量、人均年排放量、人均向大气年排放量、本地污染指数、人均本地污染指数和地均本地污染指数作比较指标,对中国二噁英排放清单(以2004年为基准年)和基准年相近的27个国家的二噁英排放清单进行了比较研究.结果表明,中国二噁英的年总排放量、向大气年排放量和本地污染指数较大,表明开展二噁英减排工作势在必行;同时,人均年排放量、人均向大气年排放量、人均本地污染指数和地均本地污染指数较小,表明中国的二噁英人均产污水平远低于其他国家,开展二噁英减排有利于实现对二噁英污染的及早控制.     

沈阳市环境空气不同功能区二噁英含量与暴露风险分析

以沈阳市不同功能区为研究对象,进行不同功能区的二噁英含量与暴露风险分析.研究表明:沈阳市不同功能区的二噁英质量浓度大小顺序为工业区＞居民区＞文化区＞商业区＞公园＞风景区;6个功能区均检测出多氯二苯并二噁英(PCDDs)、多氯二苯并呋喃(PCDFs)和多氯联苯(PCB)3种污染物,除风景区外,PCDFs所占比例最大,PCDDs居第二位,PCB所占的比例最小;毒性当量的计算结果表明,不同功能区的二噁英毒性当量浓度与其质量浓度大小顺序一致;呼吸暴露量计算结果表明,儿童的呼吸暴露量高于成人,说明儿童受到空气二噁英的呼吸暴露风险更大.     

含硫化合物对氯苯和二噁英的抑制作用

为有效控制废物焚烧过程中氯代有机污染物的排放,利用管式炉及某实际医疗废物焚烧炉研究了含硫添加剂对氯苯和二噁英的抑制,并分析了抑制剂对氯化反应的影响。结果表明,硫代硫酸钠是非常有效的抑制剂,对氯化反应的抑制率达90%;在实际焚烧炉应用上,单质硫对五氯苯、六氯苯和二噁英均存在抑制能力。     

Curbing dioxin emissions from municipal solid waste incineration in China: Re-thinking about management policies and practices

As one of the countries with large amounts of dioxin releases, the control of dioxins is a major challenge for China. Municipal solid waste (MSW) incineration should be considered a high priority source of dioxin emissions because it is playing an increasingly more important role in waste management. MSW incineration in China has much higher emission rates of dioxins than in the developed countries, partially resulting from the gaps in the technologies of incineration and flue gas cleaning. Moreover, the current management policies and practices also contribute significantly to the problem. We recommend lowering dioxin emission standard, strengthening fly ash management, and improving regulation enforcement to reduce dioxin releases into the environment from MSW incineration. We also propose that alternative strategies should be considered on dioxin control and call for an expansion of economic instruments in waste management to reduce waste generation and thus the need for incineration.     

Isoprene emission from tropical trees in Okinawa Island, Japan

This study surveyed isoprene emission from 42 indigenous and exotic tropical trees in subtropic Okinawa, Japan. Of the 42 trees studied, 4 emitted isoprene at a rate in excess of 20 μg g⁻¹ h⁻¹, and 28 showed the rates of 1–10 μg g⁻¹ h⁻¹. The remainder emitted less than 1 μg g⁻¹ h⁻¹. The majority of trees in this study may therefore fall within the lower emitting species. However, species in Moraceae that is indigenous in Okinawa emitted isoprene at relatively higher rates with an average of 14.2 μg g⁻¹ h⁻¹. The highest emission rate of 107.1 μg g⁻¹ h⁻¹ for Ficus virgata yielded the area basis rate of 47.4 nmol m⁻² s⁻¹, which is almost equivalent to the rate of high emitting species. Furthermore, a linear relationship between light intensity and isoprene emission was noted with Ficus virgata up to 1700 μmol m⁻² s⁻¹. These findings may show the potential importance of subtropical areas as sources of isoprene to the atmosphere.     

Octachlorinated dioxin in pulps and effluents: Where does it come from?

Studies on the formation/destruction of dioxins associated with the pulping of wood artificially impregnated with an industrial grade of pentachlorophenol lend support to an earlier observation that ambient dioxins deposition may not necessarily be a unique source of the higher chlorinated dioxins occasionally found in pulps and final effluent discharges. These dioxins, which seemingly occur in products from a wide range of pulping technologies including recycle operations, may also originate from pentachlorophenol-based fungicides.     

PCDDs, PCDFs, and coplanar PCBs in wild terrestrial mammals from Japan: congener specific accumulation and hepatic sequestration

The present study determined the contamination levels and congener-specific accumulation features of dioxins and related compounds (DRCs) in wild terrestrial mammals such as large Japanese field mice (LJFM), lesser Japanese moles (LJMs), and raccoon dogs (RDs) collected from Kanto region in Japan during 2001. The toxic equivalent quantity (TEQ) levels in the carcasses or adipose tissues were in the order of RDs > or = LJMs > LJFM. Comparison of DRC congener profiles in the three species and principal component analysis (PCA) demonstrated a higher contribution of OCDD, T4CB77, and P5CB118 in LJMs. Analysis of liver-adipose distribution of DRC congeners in RDs showed that livers contained significantly higher TEQs than adipose tissues, indicating that liver is a depository organ and critical for determining the toxicokinetics of DRCs. As for most T4, P5, H6CDD/DFs and for P5CB126, H6CB169 and mono-ortho PCB congeners, their liver/adipose concentration ratios in RDs revealed a tendency to increase with hepatic TEQ levels, suggesting TEQ-dependent hepatic sequestration.     

Update of daily intake of PCDDs, PCDFs, and dioxin-like PCBs from food in Japan

Total diet study (TDS) samples of 14 food groups from 16 locations in Japan, collected in 1999 and 2000, were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) to estimate the update of daily intake of these contaminants from food. The mean daily intake of toxic equivalency (TEQ) for an adult weighing 50 kg, calculated at non-detected isomer concentrations equal to zero (ND=0), was estimated to be 2.25 pg TEQ/kg b.w./day. When non-detected isomer concentrations are assumed to be equal to half of the limits of detection (ND=1/2 LOD), the mean daily intake was estimated to be 3.22 pg TEQ/kg b.w./day. These values were below the tolerable daily intake (TDI) of 4 pg TEQ/kg b.w. for PCDD/Fs and dioxin-like PCBs set in Japan. In both the estimates, the mean daily intakes were highest from fish and shellfish (76.9% at ND=0 and 53.9% at ND=1/2 LOD of the total TEQs), followed by those from meat and eggs (15.5% at ND=0 and 11.7% at ND=1/2 LOD of the total TEQs). Congener specific data revealed that these total TEQ levels were dominated by 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3^′,4,4^′,5-PeCB in each case (71.7% at ND=0 and 63.1% at ND=1/2 LOD of the total TEQs). The dioxin-like PCBs (non-ortho and mono-ortho PCBs) accounted for about 50% of these total TEQs. These data will be very useful in the risk assessment of PCDD/Fs and dioxin-like PCBs from food in Japan.     

Examination of dioxin fluxes recorded in dated aquatic-sediment cores in the Kanto region of Japan using multivariate data analysis

Past dioxin (coplanar polychlorinated biphenyl (Co-PCB), 2,3,7,8-substituted polychlorinated dibenzo-p-dioxin (PCDD) and 2,3,7,8-substituted polychlorinated dibenzofuran (PCDF)) fluxes recorded in dated aquatic-sediment cores were analyzed using principal component analysis (PCA). The data set consisted of samples from four cores collected from the Kanto region of Japan. Time trends and spatial differences in the dioxin flux were examined, and the potential relationship to emission sources was investigated. Twenty-five compounds and 58 core slices, corresponding to the later half of the 20th century, were subjected to the analysis. The PCA of both log-transformed and maximum-value-standardized data successfully divided the dioxin compounds into a small number of groups, and three similar clusters of Co-PCBs, PCDDs and penta- to hepta-CDFs were identified. PCB formulations used in the past are judged to have been responsible for the major part of the Co-PCB flux recorded in the sediment cores. However, the relationship to emission sources needs further investigation. It is suggested that most 2,3,7,8-substituted PCDDs and PCDFs are different from Co-PCBs in their emission sources or movements in the environment. The subcore clusters obtained from the PCA of log-transformed data show that the cores from different sampling areas exhibited distinct dioxin fluxes and compositions. Common time trends among the cores were more effectively summarized by the PCA of maximum-value-standardized data focusing on relative time trends. PC scores show that recently the flux of each dioxin compound in the four cores has been generally declining after having reached a peak.     

Seasonal change of PCDDs/PCDFs/DL-PCBs in the water of Ayase River, Japan: pollution sources and their contributions to TEQ

In Japan, Ayase River is one of the most polluted rivers by PCDDs, PCDFs and dioxin-like PCBs, which are referred to as dioxins in this paper. The water samples of the river were collected once per month for a year, and dioxins were analyzed to examine the dioxin sources and their contributions to toxic equivalent (TEQ). The WHO-2006 TEQs ranged from 0.26 to 7.0 pg-TEQ L⁻¹ and the average was 2.7 pg-TEQ L⁻¹; eight of 12 samples exceeded the environmental quality standard in Japan (1.0 pg-TEQ L⁻¹). The TEQ value was high during the irrigation period from May to August. The most part of the dioxins in the river water existed in suspended solids (SS) and it seemed that the river received water with highly-dioxin-contaminated SS in the irrigation period. The homologue profiles of the water samples suggested that the dioxins were influenced by pentachlorophenol (PCP) and chlornitrofen (CNP) formulations which were widely used as herbicides for the paddy fields in Japan. According to TEQ apportionment estimated by using indicative congeners, the TEQ was mainly contributed by PCP. Moreover, it was also shown that the TEQ contributions of PCP and CNP formulations increased along with the increase of the total TEQ and the TEQ contribution was dominated by these herbicides during the irrigation period. Therefore, it was concluded that the herbicides-originated dioxins run off from the paddy fields into the river during the irrigation period and increased the dioxins level in the river water. The result from the principal component analysis was consistent with these conclusions.     

Human intake of PCDDs, PCDFs, and dioxin like PCBs in Japan, 2001 and 2002

PCDDs, PCDFs, and dioxin like PCBs (dioxin) surveillance results derived from regular environmental monitoring as well as other dioxin surveys by national and local governmental bodies in Japan were collected and analyzed. Several thousand data for air and soil in fiscal year 2001 (from 01/04/2001 to 31/03/2002) and 2002, water (from the sea, rivers and lakes), sediment (from the sea, rivers and lakes), ground water, aquatic organisms, purified water from water purification plants, raw water from water purification plants, human breast milk, and human blood in fiscal 2001, and total diet study (TDS) and various kinds of foodstuff in fiscal 1998-2002 were collected. Average human uptake of dioxin in Japan in fiscal 2001 was estimated at 1.68 pg-TEQ/kg-bw/day, while uptake in fiscal 2002 was estimated at 1.52 pg-TEQ/kg-bw/day. Diet accounted for more than 90% of the total intake. Contributions of inhalation and soil ingestion were relatively small. Age-group-specific contribution of various foodstuff to total dietary intake was also estimated. The estimates of intake through fish and shellfish accounted for approximately 45-70% of total dietary intake in each age group. Monte Carlo simulation was conducted, using the data of the air and soil concentrations in fiscal 2001 and the total diet study data in fiscal 1998-2001, in order to obtain information on the variability of dioxin intake; The estimated average, median, 5th percentile and 95th percentile of the intake distribution were 1.78, 1.69, 0.95 and 2.91 pg-TEQ/kg-bw/day, respectively. This study found that the average total intake estimates in Japan in both fiscal 2001 and 2002 were estimated to be below tolerable daily intake level (TDI) defined by the Ministry of Health, Labour and Welfare, Japan (i.e. 4 pg-TEQ/kg-bw/day). The 95th percentile of the dioxin intake distributions estimated with Monte Carlo simulation using the data of the air and soil concentrations in fiscal 2001 and TDS data in fiscal 1998-2001 was also below the Japanese TDI.     

Contamination and emission factors of PCDD/Fs, unintentional PCBs, HxCBz, PeCBz and polychlorophenols in chloranil in China

The production of chloranil is regarded as a potentially significant source of unintentional POPs. This research aimed to identify the contamination levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), hexachlorobenzene (HxCBz), pentachlorobenzene (PeCBz) and polychlorophenols in chloranil samples and identify the formation pathways. The toxicity equivalent (TEQ) values for PCDD/Fs in the chloranil samples ranged from 163 to 1 540 200 pg I-TEQ g⁻¹, while the PCB TEQ values ranged from 1.9 to 3.3 pg WHO-TEQ g⁻¹. High levels of HxCBz, PeCBz and polychlorophenols were also detected in the chloranil samples. The average emission factors were 522.2 mg I-TEQ t⁻¹ (PCDD/Fs), 0.0026 mg WHO-TEQ t⁻¹ (PCBs), 32.6 mg t⁻¹ (HxCBz), and 136.6 mg t⁻¹ (PeCBz). The PCDD/Fs and PCBs are thought to be formed from the polychlorophenols and polychlorobenzenes generated during the chloranil production process. Purification of the chloranil products can reduce the unintentional POPs releases and protect the environment.     

Recent survey and effects of cooking processes on levels of PCDDs,PCDFs and Co-PCBs in leafy vegetables in Japan

We report here the latest levels of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) and coplanar polychlorinated biphenyls (Co-PCBs) in leafy vegetables in Japan as well as the effect of cooking processes on the reduction of these contaminants. Three kinds of leafy vegetables (“komatsuna”, lettuce and spinach) from seven districts in Japan in 1998 were analyzed for the 2,3,7,8-chlorine substituted PCDD/Fs and three non-ortho-PCBs (#77, 126 and 169). The mean total TEQ levels (using the WHO-TEFs) in the komatsuna, lettuce and spinach were 0.094, 0.025 and 0.196 pg/g fresh weight, respectively. The TEQ levels are dominated by 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3^′,4,4^′,5-PeCB in many of the samples. For one of these isomers, the 2,3,4,7,8-PeCDF TEQ levels showed good correlation with the total TEQ levels in the samples (r=0.957). This suggests that 2,3,4,7,8-PeCDF may be an indicator for dioxin contamination in the analysis of the leafy vegetables. Also, the effects of two cooking processes (washing and washing followed by boiling) on the dioxin levels in two types of spinach samples were investigated. On average, in both samples, the total concentrations of the PCDDs, PCDFs and Co-PCB were reduced to about 38%, 73% and 88% of the initial concentrations by washing, and to 21%, 35% and 61% of the initial concentrations by washing followed by boiling. The total TEQ levels were reduced to about 30% of the initial TEQ levels by washing followed by boiling. Significant reductions in the TEQ levels were observed in the cooked samples. Thus, the cooking processes may reduce the risk of dioxin intake from the leafy vegetables.