Substituting missing data in compositional analysis

Multivariate analysis of environmental data sets requires the absence of missing values or their substitution by small values. However, if the data is transformed logarithmically prior to the analysis, this solution cannot be applied because the logarithm of a small value might become an outlier. Several methods for substituting the missing values can be found in the literature although none of them guarantees that no distortion of the structure of the data set is produced. We propose a method for the assessment of these distortions which can be used for deciding whether to retain or not the samples or variables containing missing values and for the investigation of the performance of different substitution techniques. The method analyzes the structure of the distances among samples using Mantel tests. We present an application of the method to PCDD/F data measured in samples of terrestrial moss as part of a biomonitoring study.     

Thermodynamic investigation of the effect of oxygen and hydrogen chloride potential upon generation and decomposition behavior of dioxins

The thermodynamic equilibrium of the C‐H‐O‐Cl system has been calculated to elucidate the generation and decomposition behavior of dioxins, and is discussed from the viewpoint of the oxygen and hydrogen chloride potential. The dioxins behavior is greatly dependent on the oxygen potential, i.e. higher temperature and oxygen potential lead to the complete decomposition of dioxins, while low hydrogen chloride potential under insufficient oxygen condition leads to an increase of multi‐chlorine displacement of dioxins.     

湖鲟(Acipenser fulvescens)早期生命阶段对2,3,7,8-四氯二苯并-p-二恶英和3,3''4,4''5-五氯联苯的敏感性研究

自20世纪中叶以来，五大湖区的水生食物网就已受到多氯联苯化合物(PCBs)的污染。对于长寿命鱼类，如湖鲟(Acipenser fulvescens)，由于缺乏该物种的相对敏感性信息，一直无法确定其PCB暴露的风险。本文的研究目标就是评估湖鲟早期生命阶段对3,3''4,4''5-五氯联苯(PCB-126)或2,3,7,8-四氯二苯并-p-二恶英(TCDD)暴露的敏感性。死亡率、生长、形态和组织病理学、游泳能力和活动水平都被用作评估终点。心包和卵黄囊水肿、管状心脏、卵黄囊出血和体长较小是TCDD和PCB-126暴露中最常见的病理症状，早在受精4 d后就开始出现，其中许多的病理都以一种剂量依赖的方式发生。湖鲟体内PCB-126和TCDD的半致死剂量分别为5.4 ng/g egg(95%置信区间，3.9-7.4 ng/g egg)和0.61 ng/g egg (0.47-0.82 ng/g egg)。由此产生的PCB-126的相对强度因子(0.11)远大于世界卫生组织对鱼的估计值(毒性当量因子=0.005)，这表明目前的风险评估可能低估了PCB对湖鲟的毒性。在受精60 d后，从半致死剂量中幸存的湖鲟的游泳活性和耐力均有所下降。阈值和半数效应毒性值表明，与在北美发现的另一种鲟鱼属Scaphirhynchu相比，湖鲟对PCB和TCDD更为敏感。事实上，在大湖区和其他地方的湖鲟种群都容易受到PCB/ TCDD诱导,使胚胎发育受到影响，游泳能力下降。
精选自Tillitt, D. E., Buckler, J. A., Nicks, D. K., Candrl, J. S., Claunch, R. A., Gale, R. W., Puglis, H. J., Little, E. E., Linbo, T. L. and Baker, M. (2017), Sensitivity of lake sturgeon (Acipenser fulvescens) early life stages to 2,3,7,8-tetrachlorodibenzo-P-dioxin and 3,3′,4,4′,5-pentachlorobiphenyl. Environmental Toxicology and Chemistry, 36: 988–998. doi: 10.1002/etc.3614
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.3614/full
     

Blood dioxin biomonitoring to assess local residents' exposure from a large urban remediation project

Background

A total of 265 000 m³ of dioxin contaminated soil and sediments from past industrial activity was treated on site in an urban setting in Sydney, Australia. To respond to local community concerns about potential dioxin exposure from fugitive emissions a human biomonitoring study was undertaken.

Objective

To determine whether local residents were exposed to significant amounts of dioxin from the remediation process.Methods: Blood samples were collected from local residents around the site and a representative metropolitan control group. They were pooled within age and sex strata and the change in dioxin concentrations over the remediation period and a summary of the mid point and post remediation dioxin concentrations were compared between groups. Information on dietary intake was collected to look for possible confounding.

Results

The mean dioxin Toxic Equivalent concentrations (TeQ) decreased among both the local resident and control groups over the remediation period by 1.9 and 2.1 pg gm⁻¹ lipid respectively. Modelled blood concentrations adjusting for age and sex did not detect a significant difference between groups for changes in either TeQ or 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8 TCDD). The summary measure approach did however demonstrate that the 2,3,7,8 TCDD concentrations among the local resident group was approximately 0.7 pg g⁻¹ lipid higher compared to the control group post remediation. There were no significant changes in dietary intake sources of dioxin.

Conclusion

Biomonitoring demonstrated that local residents were not exposed to significant quantities of dioxin. Large scale remediation of dioxin contaminated land can be safely undertaken in an urban setting.     

Decreased PCDD/F formation when co-firing a waste fuel and biomass in a CFB boiler by addition of sulphates or municipal sewage sludge

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed during waste incineration and in waste-to-energy boilers. Incomplete combustion, too short residence times at low combustion temperatures (<700 °C), incineration of electronic waste and plastic waste containing chlorine are all factors influencing the formation of PCDD/Fs in boilers. The impact of chlorine and catalysing metals (such as copper and iron) in the fuel on PCDD/F formation was studied in a 12 MW_th circulating fluidised bed (CFB) boiler. The PCDD/F concentrations in the raw gas after the convection pass of the boiler and in the fly ashes were compared. The fuel types were a so-called clean biomass with low content of chlorine, biomass with enhanced content of chlorine from supply of PVC, and solid recovered fuel (SRF) which is a waste fuel containing higher concentrations of both chlorine, and catalysing metals. The PCDD/F formation increased for the biomass with enhanced chlorine content and it was significantly reduced in the raw gas as well as in the fly ashes by injection of ammonium sulphate. A link, the alkali chloride track, is demonstrated between the level of alkali chlorides in the gas phase, the chlorine content in the deposits in the convection pass and finally the PCDD/F formation. The formation of PCDD/Fs was also significantly reduced during co-combustion of SRF with municipal sewage sludge (MSS) compared to when SRF was fired without MSS as additional fuel.     

Thermal decomposition of electronic wastes: mobile phone case and other parts

Pyrolysis and combustion runs at 850°C in a horizontal laboratory furnace were carried out on different parts of a mobile phone (printed circuit board, mobile case and a mixture of both materials). The analyses of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorodibenzo-p-dioxin, polychlorodibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regarding semivolatile compounds, phenol, styrene, and its derivatives had the highest yields. In nearly all the runs the same PAHs were identified, naphthalene being the most common component obtained. Combustion of the printed circuit board produced the highest emission factor of PCDD/Fs, possibly due to the high copper content.     

Distribution of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, dioxin-like polychlorinated biphenyl and polycyclic aromatic hydrocarbons in the sediment of Temsah lake, Suez Canal, Egypt

Lake Temsah is one of the main wetlands in the Suez Canal region, and the main source for fish for the area. The lake is the end-point of several wastewater effluents. In the present study, residues of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyl (PCB) and polycyclic aromatic hydrocarbons (PAH) were monitored in the sediment of the lake. Samples were collected from six different sampling stations around the lake using a box-corer sampler, then kept frozen. Samples were extracted and cleaned up before residue determination was conducted using an HRGC/HRMS. An HP 6890 plus gas chromatograph was coupled to a Micromass Autospec Ultima mass spectrometer operating in EI mode at 35 eV and with a resolution of 10.000 (5% valley). PCDDs and PCDFs were detected in all sediment samples collected from various sampling stations. Results showed some progressive increase in PCDDs concentrations relevant to increase in chlorination. In the PCDD group of congeners, 1, 2, 3, 4, 6, 7, 8, 9 octa-CDD had the highest detected concentrations in all samples, while 2, 3, 7, 8 tetra-CDD showed the lowest concentrations. The World Health Organization toxicity equivalents ranged from 0.387 to 11.20 ng kg^-1 d.w. For PCDD homologues, hexa-CDD was the most dominant homologue in all sediment samples analysed. Regarding dioxin-like PCBs, results showed that IUPAC No. 118 congener, 2, 3, 4, 4, 5, pentachlorobiphenyl was the most concentrated of all detected congeners, with concentrations ranging between 0.039 and 43.201 µg kg^-1. For polycyclic aromatic hydrocarbons, benzo(b+k+j)fluoranthene had the highest concentrations in almost all sampling stations. However, fluorene was the smallest detected concentration in almost all stations. This result would indicate that PAH contamination of the lake seems to be coming from one main source in all sampling stations. The present work is the first record of PCCDs, PCCFs, and dioxin-like PCBs in the Temsah lake. The concentrations of the contaminants monitored in this study, especially those of PAHs, are rather alarming. Efforts should be made to stop point sources that contaminate the lake.     

Evaluation of the optimal washing conditions for dioxin-contaminated soils from the circumference of an incinerator

 The optimal soil-washing conditions for dioxins were estimated on a soil sample from the circumference of an incinerator in Nose City, Osaka, Japan. The solvents ethanol, methanol, and acetone, together with a surfactant (100% of each) could extract 40% of the dioxins from contaminated soil at room temperature. From among these solvents, ethanol was chosen for a study on how to optimize the extraction conditions because of its low toxicity and its economic advantages. The time-course of the agitation showed that the extraction rate increased for 1 min, and thereafter the rate decreased. Therefore, the agitation time was fixed at 1 min. To estimate the effect of temperature on the extraction rate, the extraction temperature was changed. The amount of dioxins extracted was largest at the boiling point of ethanol (78.3°C), giving about 76% extraction. Furthermore, at this temperature, almost 100% of the dioxins in the contaminated soil were extracted when the ratio of water to ethanol was 20%. Received: March 6, 2002 / Accepted: September 9, 2002     

Retention time profiling of all 136 tetra- through octa- chlorinated dibenzo-p-dioxins and dibenzofurans on a variety of Si-Arylene gas chromatographic stationary phases

The applicability of three different Silphenylene Silicone co-polymer (Si-Arylene) GC stationary phases (J&W Scientific DB-5ms, Varian VF-5ms, and VF-Xms) has been evaluated for the separation of all 136 tetra- through the octa- chlorinated dibenzo-p-dioxins (PCDD) and chlorinated dibenzofurans (PCDF) from closely eluting isomers using gas chromatography/high resolution mass spectrometry (GC/HRMS). Their relative performance data are compared to the “conventional” 5% diphenyl 95% dimethylpolysiloxane GC column (Supelco Equity-5) and to each other based on absolute retention times, visualized mass chromatograms, and the separation of 2,3,7,8-substituted isomers. VF-Xms GC column was able to demonstrate a better performance towards separation of 2,3,7,8-substituted PCDD/PCDF compared to other Si-Arylene GC columns tested, where only 2,3,4,7,8-PnCDF can not be resolved from 1,2,3,6,9-PnCDF and 2,3,4,6,7,8-/1,2,3,6,8,9-HxCDF and 1,2,3,7,8,9-/1,2,3,4,8,9-HxCDF can be at least partially resolved. These data suggest that the development of a single GC column for the separation of all 17 2,3,7,8-substituted dioxins and furans is feasible, which therefore could be used as a standard tool for the PCDD/PCDF methods globally including USEPA methods 1613b, 8290A, 8280B, European Standard Method EN 1948, Canadian methods DFPCB-E3418, EPS 1/RM/19, Japanese methods JIS K0311 and JIS K0312. Having one specific GC column to separate all 2,3,7,8-substituted PCDD/PCDF will significantly improve the data quality, comparability by the various methods and assessment techniques while simultaneously leading to a more cost and time efficient operation.     

Sources and distribution of polychlorinated-dibenzo-p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo-p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.