Levels of PCDDs and PCDFs in products and effluent from the Swedish pulp and paper industry and chloralkali process

Within the Swedish Dioxin Survey various samples from the pulp and paper industry and the chloralkali process have been analyzed by congener specific analytical methods. In addition to the generally discussed “bleaching pattern” of the tetrachlorinated congeners, these samples also contained higher chlorinated congeners like hexa-CDDs, hepta-CDFs, octa-CDD and octa-CDF. Consequently it is recommended that samples from the pulp industry should be analyzed for all PCDDs and PCDFs (tetra- through octa-). Counted as Nordic Toxic Equivalents (NTEQ), the recycled pulp samples had the highest contamination level followed by TMP, unbleached sulfite and bleached softwood and hardwood. In addition to the bleaching process, various chemicals used in the pulping, bleaching and wastewater treatment can contribute to the contamination.     

Evaluation of Organochlorine Compounds (PCDDs,PCDFs, PCBs and DDTs) in Two Raptor Species Inhabiting a Mediterranean Island in Spain (8 pp)

Background Species that are at high levels of the food web have often been used as bioindicators to evaluate the presence of persistent contaminants in ecosystems. Most of these species are long-lived, so pollutant burdens may be integrated in some complex way over time. This makes them particularly sensitive to deleterious effects of Persistent Organic Pollutants (POPs). Birds have been suggested as useful organisms for monitoring pollutant levels. Traditionally such studies have been carried out with raptors such as osprey (Pandion haliaetus), peregrine falcon (Falco peregrinus), bald eagle (Haliaetus leucocephalus), etc. In this paper we present the results of a monitoring study conducted on two raptor species, osprey (Pandion haliaetus) and red kite (Milvus milvus), inhabiting a Mediterranean island (Menorca, Spain). These two species have different feeding habits; ospreys prey on fish and red kites feed on terrestrial species. This study constitutes a good opportunity to investigate if differences in feeding habits (aquatic vs. terrestrial) influences the contaminants pattern in two species inhabiting the same area. Methods The study was conducted in a non-destructive way, using only failed eggs, to avoid the damage of the population stability. Eggs were collected during the period 1994–2000. The contaminants examined were dichlorodiphenyltrichloroethanes (DDTs, including DDT and its main metabolite, DDE), polychlorinated biphenyls (PCBs), including ortho PCBs (PCBs with at least one Chlorine atom in the ortho position): #28, 52, 95, 101, 123+149, 118, 114, 153, 132+105, 138, 167, 156, 157, 180, 170, 189, 194; and non ortho PCBs (PCBs with no Chlorine atom in the ortho position): #77, 126, 169 and all the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) with Chlorine atoms at the 2,3,7 and 8 position (2,3,7,8-substituted PCDDs and PCDFs). The analysis of organochlorine compounds was performed using a sample treatment based on a Solid Phase Matrix Dispersion procedure. Ortho PCBs and DDTs were determined by HRGC-μECD; non ortho PCBs and PCDD/Fs were determined by HRGC-HRMS. Results and Discussion The sum of the ortho PCB congeners analysed ranged from 0.94 to 15.03 μg/g wet weight (ww) for ospreys and from 1.0 to 11.2 μg/g ww for red kites. In both species, PCB congeners #153, #138 and #180 accounted about 75% to total ortho PCB concentrations. Regarding non ortho PCBs, for ospreys, concentrations ranged from 0.16 to 1.39 ng/g wet weight (ww) and for red kites from 0.12 to 0.51 ng/g ww, being congener #126 the most abundant. Concerning DDTs, concentration for ospreys ranged from 0.07 to 1.03 μg/g ww; and for red kites ranged from 0.90 to 2.10 μg/g ww, representing DDE more than 95% of the total DDTs, which proves a past use of DDT in the study area. Differences in contaminant levels between species are probably associated to feeding habits. The fish-eating species presents the highest PCB levels, whereas the terrestrial species exhibits the highest DDT levels. PCDD/Fs in ospreys were in the range 2.6–14.2 pg/g ww, while in red kites the range was slightly wider (22.2–43.2 pg/g ww), being PCDDs the major contributors in black kites. Ospreys had PCDDs similar to PCDF concentrations. PCDD/F profiles were mostly influenced by OCDD in both species. Non ortho PCBs were the major contributors to calculated Toxic Equivalent Quantity (TEQs) in both species. Conclusion In both species studied, ortho-PCBs could represent a problem of concern since 57% of the eggs exhibited levels higher than 4 μg/g ww, reported as the level that could cause reduced hatchability, embryo mortality, and deformities in birds. Recommendations and Outlook Results found in this study suggest that a more detailed study to clear up possible deleterious effects of PCBs on the bird populations studied here should be done. Section Editor: Prof. Dr. Paola Gramatica (paola.gramatica@uninsubria.it)     

辽宁省部分城市空气中二(口恶)(口英)含量测定及结果分析

对辽宁省部分城市环境空气中二(口恶)(口英)类物质含量的测定结果表明,该地区环境空气中二(口恶)(口英)含量在0.07～1.0pg TEQ/m3之间.     

碱性及含硫化合物对十溴联苯醚热降解的影响

将十溴联苯醚（BDE-209）于400~600℃的温度范围内进行热降解,利用GC、GC/MS对产物种类及含量变化进行分析,讨论了温度、时间、碱性化合物和含硫化合物对BDE-209降解以及对溴代二噁英生成的影响.结果表明.温度和时间均是BDE-209热降解和生成溴代二噁英的重要影响因素;热降解40min时,450℃条件下溴代二噁英生成量最多;产物种类证实碱性化合物通过与BDE-209脱溴形成的HBr反应促进降解,且可抑制二噁英的生成;含硫化合物的添加同样促进BDE-209降解,抑制二噁英的形成,其详细的抑制机理有待进一步确定,BDE-209的降解反应有两种情况,即苯环上的脱溴反应和醚键的断裂反应.     

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid–liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25–25 µg L^?1 of 1.25–20 µg L^?1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.     

控制城市垃圾焚烧二噁（口英）产生与扩散方法

控制垃圾焚烧二产生与扩散分三部分首先,通过预处理除去原生垃圾中的聚氯乙烯塑料,从源头上控制垃圾焚烧二哄产生的物质基础;其次,垃圾焚烧炉采用组合式循环流化床锅炉,实行垃圾先低温热解气化,然后高温燃烧垃圾热解气体的方式,同时在炉内加入添加剂实现稳定燃烧和部分脱氯,以减少二哄在炉内生成和炉后形成量;最后,在烟气尾部采用吸附剂吸附二哄,并与布袋除尘器配套使用,控制二哄的尾部扩散.该工艺具有成本低、控污效率高等优点,特别适用于发展中国家的垃圾焚烧二哄控制.     

Metal binding capacity of soft acid,organic‐rich waters

Organic carbon from one stream and two ponds in South Carolina was fractionated into five nominal molecular diameter fractions by ultrafiltration. The concentrations associated with and binding capacity for Ca, Cd, Cu and Pb were determined for each fraction. The distribution of organic carbon among ultrafilter fractions varied from water to water, with the largest percentage occurring in the smaller fractions. Calcium was associated with each of the fractions isolated from each of the three waters, indicating Ca is bound to organics in all fractions, however, more than 99% of the Ca which passed the smallest ultrafilter was removed by cationic exchange resin. Each fraction bound more Ca than Cd, Cu or Pb except in a few cases where Pb binding was greater. All of the organic fractions had their Ca++ binding sites saturated. Calcium was not an effective competitive ion against Cd, Cu or Pb for organic binding sites. The total Cu binding capacity was less than that of Ca or Pb but similar to that of Cd. Naturally occurring organics bound more Pb than Cd or Cu but less than Ca. Saturation of Cu binding sites was less than 20% in most ultrafilter fractions except that with a nominal molecular weight of between 10,000 and 300,000 where the percent of saturation was as much as 60%. Approximately 50% of the Cu was removed onto anionic exchange resin in two waters while more than 90% was removed from water with a high organic content. Percent saturation of Cd and Pb binding sites ranged from 0.091% to 5.4% and 0.059% to 1.5%, respectively. All ions tested effectively competed with Cd, Cu or Pb for some but not all binding sites, indicating that organic binding sites were heterogeneous. A generalized order of metal‐organic stabilities based on competition for binding sites is Al>Cd>Pb>Cu>Ni = Mg=Zn = Mn>Ca. Both Cd+2 and Al+3 effectively out competed Pb++ and Cd and Pb out competed Cu for most organic binding sites.     

Study on polychlorinated dibenzo‐p‐dioxins and dibenzofurans in rivers and estuaries in Osaka Bay in Japan

In order to search the source of polychlorinated dibenzo‐p‐dioxins (PCDDs) and dibenzofurans (PCDFs) in blue mussel in Osaka bay, sediments from Osaka bay and from rivers running near an urban municipal incinerator were analysed for PCDDs, PCDFs and PCBs. The river and estuary sediments were all found to be contaminated with PCDDs at average levels of 9.8 and 12ppb on the dry basis, PCDFs of 7.8 and 5.1 ppb, and PCBs of 1600 and 1300ppb, respectively. The two sediments contained similar profiles of specific isomers and congeners of PCDDs and PCDFs with each other. In addition, there was observed positive close correlations between PCDD and PCDF levels in the two specimens as well as fly ash from urban municipal incinerators. These allow the conclusion that the main source of the two chemicals in Osaka bay is fly ash from waste incineration.     

我国二英污染水平和环境归趋模拟

运用Level Ⅲ逸度模型,研究了我国环境介质中二英的平均浓度水平和迁移规律. 比较不同尺度下的模拟结果表明,Level Ⅲ逸度模型可以应用于较大尺度的研究. 数据显示,虽然我国二英排放总量较大,但是环境介质中TEQ(指二英毒性当量质量浓度)平均值仍处于较低水平,大气中TEQ平均值仅为4.26～15.10 fg/m3,土壤中TEQ平均值为0.013 5～0.115 0 pg/g,沉积物中TEQ平均值为0.445～2.300 pg/g. 达到稳态时二英的外界输入影响较大,且主要的迁移过程是从大气到土壤.      

二噁英类减排的国际动向和我国的战略构想

二噁英类减排是履行<关于持久性有机污染物的斯德哥尔摩公约>的重点和难点.本文在分析日本、美国、欧盟等发达国家在二噁英类减排控制方面成功经验的基础上,结合国际上的最新动向和我国二噁英类问题的实际特点,提出了解决我国二噁英类问题的初步战略构想.