GC-PID联用直接测定大气中痕量烃类化合物

作者把气相色谱仪(GC)与自行研制的光离子化检测器(PID)联用,实现了大气中痕量烃类化合物的直接测定,给出了仪器的构成和性能指标及测量结果.     

Identification of sources of elevated concentrations of polycyclic aromatic hydrocarbons in an industrial area in Tianjin, China

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatography equipped with a mass spectrometry detector in 105 topsoil samples from an industrial area around Bohai Bay, Tianjin in the North of China. Results demonstrated that concentrations of PAHs in 104 soil samples from this area ranged from 68.7 to 5,590 ng g^???1 dry weight with a mean of ∑16PAHs 814 ± 813 ng g^???1, which suggests that there exists mid to high levels of PAH contamination. The concentration of ∑16PAHs in one soil sample from Tianjin Port was exceptionally high (48,700 ng g^???1). Ninety-three of the 105 soil samples were considered to be contaminated with PAHs (>200 ng g^???1), and 25 were heavily polluted (>1,000 ng g^???1). The sites with high PAHs concentration are mainly distributed around chemical industry parks and near highways. Two low molecular weight PAHs, naphthalene and phenanthrene, were the dominant components in the soil samples, which accounted for 22.1% and 10.7% of the ∑16PAHs concentration, respectively. According to the observed molecular indices, house heating in winter, straw stalk combustion in open areas after harvest, and petroleum input were common sources of PAHs in this area, while factory discharge and vehicle exhaust were the major sources around chemical industrial parks and near highways. Biological processes were probably another main source of low molecular weight PAHs.     

Perfluorinated compounds in the Pearl River and Yangtze River of China

A total of 14 perfluorinated compounds (PFCs) were quantified in river water samples collected from tributaries of the Pearl River (Guangzhou Province, south China) and the Yangtze River (central China). Among the PFCs analyzed, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the two compounds with the highest concentrations. PFOS concentrations ranged from 0.90 to 99 ng/l and <0.01–14 ng/l in samples from the Pearl River and Yangtze River, respectively; whereas those for PFOA ranged from 0.85 to 13 ng/l and 2.0–260 ng/l. Lower concentrations were measured for perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctanesulfoamide (PFOSA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorononaoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA). Concentrations of several perfluorocarboxylic acids, including perfluorododecanoic acid (PFDoDA), perfluorotetradecanoic acid (PFTeDA), perfluorohexadecanoic acid (PFHxDA) and perfluorooctadecanoic acid (PFOcDA) were lower than the limits of quantification in all the samples analyzed. The highest concentrations of most PFCs were observed in water samples from the Yangtze River near Shanghai, the major industrial and financial centre in China. In addition, sampling locations in the lower reaches of the Yangtze River with a reduced flow rate might serve as a final sink for contaminants from the upstream river runoffs. Generally, PFOS was the dominant PFC found in samples from the Pearl River, while PFOA was the predominant PFC in water from the Yangtze River. Specifically, a considerable amount of PFBS (22.9–26.1% of total PFC analyzed) was measured in water collected near Nanjing, which indicates the presence of potential sources of PFBS in this part of China. Completely different PFC composition profiles were observed for samples from the Pearl River and the Yangtze River. This indicates the presence of dissimilar sources in these two regions.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd,) and Al concentrations as well as values of Ca/Al in the tip, middle and base sections, and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

Heavy metals in bark of <Emphasis Type="Italic">Pinus massoniana</Emphasis> (Lamb.) as an indicator of atmospheric deposition near a smeltery at Qujiang,China

Goal, Scope and Background Rapid urbanization and the expansion of industrial activities in the past several decades have led to large increases in emissions of pollutants in the Pearl River Delta of south China. Recent reports have suggested that industrial emission is a major factor contributing to the damages in current natural ecosystem in the Delta area. Tree barks have been used successfully to monitor the levels of atmospheric metal deposition in many areas, but rarely in China. This study aimed at determining whether atmospheric heavy metal deposition from a Pb-Zn smeltery at Qujiang, Guangdong province, could be accurately reflected both in the inner bark and the outer bark of Masson pine (Pinus massoniana L.). The impact of the emission from smeltery on the soils beneath the trees and the relationships of the concentrations between the soils and the barks were also analyzed. Methods Barks around the bole of Pinus massoniana from a pine forest near a Pb-Zn smeltery at Qujiang and a reference forest at Dinghushan natural reserve were sampled with a stainless knife at an average height of 1.5 m above the ground. Mosses and lichens on the surface barks were cleaned prior to sampling. The samples were carefully divided into the inner bark (living part) and the outer bark (dead part) in the laboratory, and dried and ground, respectively. After being dry-ashed, the powder of the barks was dissolved in HNO₃. The solutions were analyzed for iron (Fe), manganese (Mn), copper (Cu), zinc (Zn), chromium (Cr), nickel (Ni) and cobalt (Co) by inductively coupled plasmas emission spectrometry (ICP, PS-1000AT, USA) and Cadmium (Cd) and lead (Pb) by graphite furnace atomic absorption spectrometry (GFAAS, ZEENIT 60, Germany). Surface soils (0–10 cm) beneath the sample trees were also collected and analyzed for the selected metals. Results and Discussion Concentrations of the selected metals in soils at Qujiang were far above their environmental background values in the area, except for Fe and Mn, whilst at Dinghushan, they were far below their background values, except for Cd and Co. Levels of the metals, in particular Pb and Zn, in the soils beneath the sample trees at Qujiang were higher than those at Dinghushan with statistical significance. The result suggested that the pine forest soils at Qujiang had a great input of heavy metals from wet and dry atmospheric deposition, with the Pb-Zn smeltery most probably being the source. Levels of Cu, Fe, Mn, Zn, Ni and Pb at Qujiang, both in the inner and the outer bark, were statistically higher than those at Dinghushan. Higher concentrations of Pb, Fe, Zn and Cu may come from the stem-flow of elements leached from the canopy, soil splash on the 1.5 m height and sorption of metals in the mosses and lichens growing on the bark, which were direct or indirect results from the atmospheric deposition. Levels of heavy metals in the outer barks were associated well with the metal concentrations in the soil, reflecting the close relationships between the metal atmospheric deposition and their accumulation in the outer bark of Masson pine. The significant (p<0.01) correlations of Fe-Cu, Fe-Cr, Fe-Pb, Fe-Ni, Pb-Ni, and Pb-Zn in the outer barks at Qujiang again suggested a common source for the metals. The correlation only occurred between Pb and Ni, Cd and Co in the outer barks at Dinghushan, which suggested that those metals must possibly have other uncommon sources. Conclusions Atmospheric deposition of the selected metals was great at Qujiang, based on the levels in the bark of Pinus massoniana and on the concentrations in the soils beneath the trees compared with that at Dinghushan. Bark of Pinus massoniana, especially the outer bark, was an indicator of metal loading at least at the time of sampling. Recommendations and Perspectives The results from this study and the techniques employed constituted a new contribution to the development of biogeochemical methods for environmental monitoring particularly in areas with high frequency of pollution in China. The method would be of value for follow up studies aimed at the assessment of industrial pollution in other areas similar with the Pearl River Delta.     

Source analysis of particulate-phase polycyclic aromatic hydrocarbons in an urban atmosphere of a northern city in China

Particle-associated polycyclic aromatic hydrocarbon (PAH) concentrations were investigated at six sampling sites in the heating (February to March 2001) and nonheating (August to September 2001) periods in an industrial city in Northern China. Thirteen PAHs were measured. The total average concentrations (nanograms per meter cubed) of PAHs ranged between 78.93 and 214.63 during the heating period and from 31.48 to 102.26 in the nonheating period. Benzo(a)pyrene occurred at the highest level at a site near an industrial area but occurred at low concentrations far from the city center and industrial areas. In addition, ambient PAH profiles were studied. The five and six-ring species occurred in high fractions at the sampling site. By diagnostic ratio analysis, the major source at each sampling site in the city was coal combustion in the heating period; in the nonheating period, the major sources were relatively complex. Finally, the similarities among the six regions were assessed by principal component analysis, cluster analysis, and coefficient of divergence. These multivariate statistical analyses produced similar results, which agreed with the results from the diagnostic ratio analysis.     

水体环境中氟喹诺酮类药物的污染现状及分析方法

阐述了水体环境中的氟喹诺酮类（FQs）药物的来源和污染现状,介绍了FQs在水体环境中的迁移、转化和转归途径,归纳了各种当前使用较多的FQs分析检测方法的功能特点和适用条件。指出今后在FQs分析技术的开发上,应注重提高检测容量、降低检出限和削减环境负面影响因素。     

CTAB改性蒙脱石负载锰氧化物催化剂的原位生长法制备及其低温SCR脱硝活性研究

以十六烷基三甲基溴化铵(CTAB)改性的有机蒙脱石(OMMT)为载体,采用原位生长法一步合成负载型锰氧化物催化剂(MnOx/OMMTSP),并应用于低温NH3-SCR脱硝反应.考察了表面有机官能团对催化剂脱硝活性的影响,发现载体表面有机官能团对催化剂的低温SCR活性具有显著的抑制作用.对有机蒙脱石载体负载锰氧化物前后分别进行热处理以去除表面有机官能团,可有效提高催化剂活性.同时,通过XRD、SEM、TEM、BET、XPS、TG、NH₃-TPD和H₂-TPR等表征手段对催化剂的结构和及理化特性进行了表征.结果表明,在原位生长法制备催化剂的过程中,有机官能团的存在主要影响了前驱体物种在载体表面的原位反应,从而影响了活性物种的化学性质;其次,有机官能团本身也对SCR反应具有抑制作用,但影响较小.分析发现,有机官能团的存在抑制了原位生长过程中Mn⁴⁺的生成,而将催化剂在氧气氛围下进行煅烧处理,不但使催化剂的比表面积大幅提升,而且增加了其Mn⁴⁺比例,可显著增强催化剂的酸中心数量及氧化还原能力.     

试论生态文明制度体系的构建

建立健全生态文明制度体系是推进我国生态文明建设的重点。党的十八届三中全会通过的《中共中央关于全面深化改革若干重大问题的决定》指出,生态文明制度体系应当包括决策制度、评价制度、管理制度与考核制度等内容。立足社会主义制度建设的中国特色,针对我国生态文明建设的具体需求,本文将生态文明制度体系解构为四大板块:绿色高效决策制度、生态有价评估制度、生态环境监管制度与生态优先考核制度,并进一步明确了各项制度构建工作的具体内容。生态文明制度体系的构建和不断完善,将为全面建成人与自然和谐的美丽中国提供系统保障。