Theoretical study on the formation mechanism of polychlorinated dibenzothiophenes/thianthrenes from 2-chlorothiophenol molecules

Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes(PCDT/TAs),sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans(PCDD/Fs), has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol(2-CTP) as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene(1-MCTA), 1,6-dichlorothianthrene(1,6-DCTA), 4,6-dichlorodibenzothiophene(4,6-DCDT)and 1,6-dichlorodibenzothiophene(1,6-DCDT). The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.     

基于地理加权回归的NO2排放预测模型

为了探究影响NO2排放的交通相关因素,以交通分析小区为基本单位,提取了美国洛杉矶城市的人口特征、道路网络特征、交通状况等数据,采用地理加权回归模型(GWR)分析各交通相关因素对NO2排放的影响,从而建立交通小区NO2排放预测模型。结果表明,交通小区路网密度、交通小区机动车吸引量、通勤时间在30~60 min的工作人数与NO2的排放呈正相关,表明3种影响因素的增加会造成NO2排放的增加;而交通小区在家工作的人数、慢行交通(步行、自行车等绿色出行方式)吸引量与NO2的排放呈负相关,表明适当鼓励在家工作的新型办公方式、鼓励居民出行选择慢行交通,能有效减少交通小区NO2的排放。     

Temperature effect on photolysis decomposing of perfluorooctanoic acid

Perfluorooctanoic acid(PFOA)is recalcitrant to degrade and mineralize.Here,the effect of temperature on the photolytic decomposition of PFOA was investigated.The decomposition of PFOA was enhanced from 34% to 99% in 60 min of exposure when the temperature was increased from 25 to 85°C under UV light(201–600 nm).The limited degree of decomposition at 25°C was due to low quantum yield,which was increased by a factor of 12 at 85°C.Under the imposed conditions,the defluorination ratio increased from 8% at 25°C to 50% at85°C in 60 min.Production of perfluorinated carboxylic acids(PFCAs,C7–C5),PFCAs(C4–C3)and TFA(trifluoroacetic acid,C2)accelerated and attained a maximum within 30 to 90 min at 85°C.However,these reactions did not occur at 25°C despite extended irradiation to180 min.PFOA was decomposed in a step-wise process by surrendering one CF2unit.In each cyclical process,increased temperature enhanced the quantum yields of irradiation and reactions between water molecules and intermediates radicals.The energy consumption for removing eachμmol of PFOA was reduced from 82.5 k J at 25°C to 10.9 k J at 85°C using photolysis.Photolysis coupled with heat achieved high rates of PFOA degradation and defluorination.     

Aerobic N2O emission for activated sludge acclimated under different aeration rates in the multiple anoxic and aerobic process

Nitrous oxide (N₂O) is a potent greenhouse gas that can be emitted during biological nitrogen removal. N₂O emission was examined in a multiple anoxic and aerobic process at the aeration rates of 600 mL/min sequencing batch reactor (SBR_L) and 1200 mL/min (SBR_H). The nitrogen removal percentage was 89% in SBR_L and 71% in SBR_H, respectively. N₂O emission mainly occurred during the aerobic phase, and the N₂O emission factor was 10.1% in SBR_L and 2.3% in SBR_H, respectively. In all batch experiments, the N₂O emission potential was high in SBR_L compared with SBR_H. In SBR_L, with increasing aeration rates, the N₂O emission factor decreased during nitrification, while it increased during denitrification and simultaneous nitrification and denitrification (SND). By contrast, in SBR_H the N₂O emission factor during nitrification, denitrification and SND was relatively low and changed little with increasing aeration rates. The microbial competition affected the N₂O emission during biological nitrogen removal.     

火电行业清洁生产与末端治理技术对二氧化硫减排效果评估

为探明清洁生产技术在我国大气污染物削减中所起的作用,本文以火电行业为例,以SO_2作为特征污染物,对“清洁生产”和“末端治理”技术进行了筛选,建立了削污和减排效果分析模型,并收集火电行业的权威统计数据,计算了火电行业“清洁生产”技术削污量与“末端治理”技术减排量及两类技术各自削减量占比情况,研究了建国以来(1949—2013年)我国火电行业清洁生产技术削污效果和末端治理技术减排效果及其演变规律,并在此基础上提出政策建议.研究结果显示,以火电行业发电效率最低的低温低压发电技术为基准线,1949—2013年65年期间电力行业通过清洁生产技术累计实现SO_2削污量为4.94亿t,节约4940亿元的环保资金投入,削污率达到58.5%;2002—2013年12年期间电力行业末端治理技术累计实现SO_2减排量为1.10亿t,减排率为13.0%.     

Effect of algal flocculation on dissolved organic matters using cationic starch modified soils

Modified soils(MSs) are being increasingly used as geo-engineering materials for the sedimentation removal of cyanobacterial blooms. Cationic starch(CS) has been tested as an effective soil modifier, but little is known about its potential impacts on the treated water.This study investigated dissolved organic matters in the bloom water after algal removal using cationic starch modified soils(CS-MSs). Results showed that the dissolved organic carbon(DOC) could be decreased by CS-MS flocculation and the use of higher charge density CS yielded a greater DOC reduction. When CS with the charge density of 0.052, 0.102 and0.293 meq/g were used, DOC was decreased from 3.4 to 3.0, 2.3 and 1.7 mg/L, respectively.The excitation–emission matrix fluorescence spectroscopy and UV254 analysis indicated that CS-MS exhibits an ability to remove some soluble organics, which contributed to the DOC reduction. However, the use of low charge density CS posed a potential risk of DOC increase due to the high CS loading for effective algal removal. When CS with the charge density of 0.044 meq/g was used, DOC was increased from 3.4 to 3.9 mg/L. This study suggested, when CS-MS is used for cyanobacterial bloom removal, the content of dissolved organic matters in the treated water can be controlled by optimizing the charge density of CS. For the settled organic matters, other measures(e.g., capping treatments using oxygen loaded materials) should be jointly applied after algal flocculation.     

烟气同时脱硫脱硝技术进展研究

中国二氧化硫和氮氧化物的排放所引起的污染越来越严重,国家治理大气污染的力度逐步加大.现阶段单独脱硫脱硝的技术已经很成熟,考虑到经济高效的问题,烟气同时脱硫脱硝技术是当前烟气净化技术研究的热点之一.研究开发经济、高效、简单的烟气脱硫脱硝一体化技术十分必要和紧迫.本文介绍了几种典型烟气同时脱硫脱硝技术原理及其研究现状,分析了其原理及优缺点,对几种工艺进行了技术和经济分析.最后对脱硫脱硝一体化技术的发展前景作了展望.     

Male takeover,infanticide, and female countertactics in white-headed leaf monkeys (<Emphasis Type="Italic">Trachypithecus leucocephalus</Emphasis>)

Infanticide by males is common in mammalian species such as primates in which lactation lasts much longer than gestation. It frequently occurs in one-male groups following male takeovers and is likely a male reproductive strategy. Reported female countertactics include abrupt weaning of infants, dispersal, or paternity confusion. Here, we estimated costs of female countertactics in terms of weaning ages and interbirth intervals. We observed a population of white-headed leaf monkeys (Trachypithecus leucocephalus) in Nongguan Nature Reserve, China (1995–2006) mainly composed of one-male groups. Takeovers (N = 11) coincided with the peak conception period. Detailed data are presented for five takeovers (34 females, 29 infants, and 47 group-years) leading to six infant disappearances (42.9% of infant mortality). All presumed infanticides were in accordance with the sexual selection hypothesis. Following a takeover, females without infants or with old infants stayed with the new males, incurring no or low costs (via abrupt weaning). Females with young infants dispersing with the old males also experienced low costs. High costs (due to infant loss) were incurred by pregnant females and those with young infants who stayed with the new males indicating that paternity was not confused. Costs in terms of long interbirth intervals were also high for females leaving with the old males to later join the new males, despite infant survival. Female countertactics reflected female philopatry mediated by infant age. Presumably due to the seasonal timing of takeovers, most countertactics seemed successful given that 32.3% of females apparently incurred no costs and 41.2% incurred only low costs.     

Polybrominated diphenyl ethers in background surface soils from the Yangtze River Delta (YRD), China: occurrence,sources, and inventory

Purposes  

Very few data for polybrominated diphenyl ethers (PBDEs) were available in the Yangtze River Delta (YRD), one of the most developed and urbanized region in China. In this study, Chongming Island, located at the estuary of the Yangtze River, was selected as background area to investigate the occurrence, sources, and inventory of PBDEs.     

失效磷酸基化学抛光液的再生

采用氟铝酸钠沉淀法去除失效磷酸基化学抛光液中的铝杂质,并对溶液再生利用的工艺条件进行了研究.实验结果表明,在氢氧化钠和氢氟酸加入量与理论值的比均为1.2(即n(氢氧化钠):n(Al~(3+)):2:1、n(氢氟酸):n(Al~(3+))=28:5)的条件下,采用二步法过滤后,抛光液中磷酸质量分数大于50%,磷酸回收率为79.5%,Al~(3+)去除率为97.1%,剩余Al~(3+)质量分数为0.05%.滤渣经处理后成为新的有价物质,滤液在补加磷酸和其他有效成分后可再生循环使用.