Potential sources of unintentionally produced PCB,HCB, and PeCBz in China: A preliminary overview

Under the Stockholm Convention on Persistent Organic Pollutants (POPs), China is required not only to reduce polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) but also unintentionally produced polychlorinated biphenyls (PCB), hexachlorobenzene (HCB) and pentachlorobenzene (PeCBz). A baseline of the sources in China that generate these unintentional POPs is needed for both research and regulation purposes. In this paper, we have compiled production data of potential sources in China and assessed them in five-year intervals from 2000 to 2015. Most of these activities experienced changes from rapid growth to slow growth. Measured data for PCB, HCB and PeCBz in samples collected from potential sources in China were reviewed. Most information was associated to thermal processes with high potential of emission, including waste incineration and ferrous and non-ferrous metal production. In addition, high levels of PCB, HCB and PeCBz were found as impurities in a few chlorinated products or as by-products in solvent production, which suggested organochlorine industry might be important sources. Finally, based on the studies reviewed, recommendations for future actions in research and policy as well as a few regulatory issues in China are discussed.

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碱催化脱氯技术处理氯代新POPs研究及示范工程

以硫丹作为氯代新POPs的代表,通过实验室小试研究,探讨反应温度、NaOH和石蜡油投加量对硫丹在NaOH/石蜡油碱催化反应体系中的去除和脱氯效率(RE和DE)的影响,并寻找出最优条件,开展示范工程研究.实验室小试结果表明,反应温度、NaOH投加量和石蜡油投加量对硫丹脱氯效率的影响要大于对其去除率的影响.当温度为250℃,硫丹和NaOH及石蜡油的质量比为1:3:6和1:3:10时,反应3h后,硫丹去除率和脱氯效率分别达到99.99%和99%以上.采用硫丹和得克隆两种氯代有机物开展示范工程研究,中试设备处理能力达到15kg/批次,在250~300℃下反应3~10h后,对硫丹和得克隆的去除效率均达到99.9%以上,表明硫丹和得克隆被有效分解.示范工程的成功实施为我国履行斯德哥尔摩公约提供技术支持.     

Can pine needles indicate trends in the air pollution levels at remote sites?

Data from ten years of integrated monitoring were used here to evaluate whether pine needles are a feasible tool for an assessment of long-term trends of the atmospheric contamination. Pine needles collected once a year were compared to high volume air samples collected for 24 h, every 7 days, and passive air samples integrated over 28-day periods. Results showed the same concentration patterns of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) captured in needles and high volume samples. Passive air samplers were less efficient in sampling the particle-bound compounds. Theoretical air volume equivalent to each needle sample (V_EQ) was calculated as a ratio of the needle concentration over the mean air concentration. Results indicated different equivalent volumes for PAHs and organochlorines, possibly due to the faster degradation rates of PAHs in needles. The most important finding is that in the long term a needle monitoring gives very similar information on temporal trends of the atmospheric pollution as does a high volume air monitoring.     

基于AHP的POPs污染控制技术评价方法研究

POPs污染控制技术的引进和推广是削减POPs排放的重要手段,对最大限度地控制我国POPs污染,提升国家履行《斯德哥尔摩公约》的能力具有重要意义。为了筛选出适合我国发展需求与经济水平的技术,在对POPs污染控制技术进行分类研究的基础上,基于层次分析法(AHP)建立了POPs污染控制技术综合评价指标体系和评价方法。同时,选择钢铁行业的两种烟气POPs控制技术进行案例分析,证明了建立的评价方法具有较好的可行性。此外,评价结果表明,高炉煤气干式除尘余压压差发电技术优于转炉煤气干法烟气除尘及尘泥压块技术,应优先考虑在钢铁行业进行应用与推广,以提升行业POPs污染控制能力。     

气氛含氧量对DDT热处理特性的影响

滴滴涕属于有机氯农药,其所含成分DDTs在环境中难以降解,并具有生物毒性。利用高温管式炉研究气氛中含氧量对滴滴涕热处理特性的影响,为研发废弃滴滴涕高温热处理技术提供理论依据。实验结果表明,在600℃时,滴滴涕去除率最高为含氧量21%时的70.48%;在900℃条件下,当含氧量为21%时DDT去除率≥99%;在1 200℃条件下,当含氧量≥12%时DDT去除率≥99.9%。在滴滴涕热处理残渣中,o,p’-DDT占DDTs总量的比例在3个温度段中都随含氧量的增加而增长,DDT则都随含氧量增加而减少,且上述变化随温度升高而幅度加大。在尾气中,p,p’-DDE占DDTs总量的比例在3个温度段中都随含氧量增加而递增,在1 200℃条件下尤为明显。     

Effects of hydrodynamics on the distribution of trace persistent organic pollutants and macrobenthic communities in Bohai Bay

In recent years, the rapid economic development along Bohai Bay, has brought out continuous increasing of the pollution loads in the Bohai Sea, especially by the large coastal reclamation project, Tianjin Binhai New Area. In the period of 2007-2009, we collected the sediments of the main rivers, estuaries, intertidal zone, and near-shore area of Bohai Bay, and Macrobenthos associated with the marine sediments to assess the influence of hydrodynamics in the coastal environment on the pattern of trace contaminants and the macrobenthic community. Based on data derived from these samples, the levels of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) in sediments followed the order PAHs > OCPs > PCBs > PBDEs. The higher concentrations of PCBs, OCPs, PAHs and PBDEs were found in the estuarine and near-shore environment of the Dagu Drainage River. The spatial distribution of OCPs was different to that of PCBs due to the direction of the velocity field of Bohai Bay in its old and new topography, and the higher water-solubility of OCPs than that of PCBs. The results of the Pearson correlation and the PCA indicate that the medium diameter (MD) of sediments was the predominant factor influencing the distribution of PCBs and OCPs, most sampling sites were characterized mainly by TOC of sediments and biomass of macrobenthos. The results indicate that the distribution of trace contaminants and macrobenthic community in Bohai Bay are mainly affected by the hydrodynamic conditions.     

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.     

QSPR for prediction of subcooled vapor pressures (log PL) of polychlorinated trans-azobenzenes

In this study the values of subcooled vapor pressures (log P_L) were estimated for 209 trans chloroazobenzenes (Ct-ABs) that fill some gaps in analytical and experimental data on these compounds. There are 209 chloro derivatives of trans azobenzenes that are relatively stable and more environmentally relevant than 209 chloro cis congeners. The calculations models were based on the Quantitative Structure-Property Relationship (QSPR) scheme using the semi-empirical method (PM6) in molecular package (MOPAC) software and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set) in Gaussian 03 software method and the artificial neural networks (ANNs) prediction. The values of log P_L predicted by models used varied between ?3.94 to ?2.66 for Mono-; ?4.85 to ?2.97 for Di-; ?5.18 to ?3.17 for Tri-; ?6.02 to ?3.77 for Tetra-; ?6.64 to ?4.64 for Penta-; ?7.36 to ?4.76 for Hexa-; ?7.54 to ?5.79 for Hepta-; ?7.75 to ?6.64 for Octa-; ?7.89 to ?7.44 for Nona-Ct-Abs; and ?8.09 and ?8.13 for Deca-Ct-AB. Based on these values Ct-ABs can be grouped localized among relatively low (log P_L ?4 to ?2) and low (log P_L < ?4) mobile Persistent Organic Pollutants (POPs). Both the calculation methods employed were characterized by similar prediction ability of subcooled vapor pressure values of Ct-ABs, while those of PM6 are much more efficient due to a cheaper hardware used and around 300-fold less time spent on calculations.     

Chemical fate,latitudinal distribution and long-range transport of cyclic volatile methylsiloxanes in the global environment: A modeling assessment

Cyclic volatile methylsiloxanes (cVMS) such as octamethycyclotetrasiloxane (D4), decamethycyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are widely used as intermediates in the synthesis of high-molecular weight silicone polymers or as ingredients in the formulation of personal care products. The global environmental fate, latitudinal distribution, and long range transport of those cVMS were analyzed by two multimedia chemical fate models using the best available physicochemical properties as inputs and known persistent organic pollutants (POPs) and highly persistent volatile organic chemicals (“fliers”) as reference. The global transport and accumulation characteristics of cVMS differ from those of typical POPs in three significant ways. First, a large fraction of the released cVMS tends to become airborne and is removed from the global environment by degradation in air, whereas known POPs have a tendency to be distributed and persistent in all media. Secondly, although cVMS can travel a substantial distance in the atmosphere, they have little potential for deposition to surface media in remote regions. This contrasts with a deposition potential of known POPs that exceeds that of cVMS by 4–5 orders of magnitude. Thirdly, cVMS have short global residence times with the majority of the global mass removed within 3 months of the end of release. Global residence times of POPs on the other hand are in years. The persistent fliers resemble the cVMS with respect to the first two attributes, but their global residence times are more like those of the POPs.     

Assessment of decadal changes in sediment contamination in a large connecting channel (Detroit River,North America)

Concentrations of selected heavy metals (Cd, Cu, Hg, Pb, Zn) and organic contaminants (PCBs, PAHs) were investigated in samples from the Detroit River (Great Lakes, North America) in 1999 and 2008/09 collected using a stratified random sampling design. Getis–Ord geospatial analysis was used to further establish locations of areas demonstrating significantly high and low contaminant concentrations in the river. Based on the stratified random sampling design, a majority of the examined metals and organic contaminants demonstrated little or no trends with respect to regional sediment concentrations and river-wide mass balances over the investigated time interval. The Getis–Ord analysis revealed local scales of contaminated and clean areas which did not conform to the original strata used in the geostatistical sampling design. It is suggested that geospatial analyses such as Getis–Ord be used in the design of future sediment quality surveys to refine locations of strata that can simultaneously address sediment recovery over system-wide, regional and local spatial scales.