固相萃取/气相色谱质谱法测定灰尘中的氯代多环芳烃

建立了固相萃取(SPE)/气相色谱质谱(GC/MS)联用检测灰尘中氯代多环芳烃(ClPAHs)的方法.以正己烷和二氯甲烷混合液为提取溶剂,索氏提取灰尘样品中的20种ClPAHs,活性硅胶层析柱与活性炭混合硅胶SPE柱协同净化.净化后的提取液采用GC/MS测定,SIM模式扫描,并用质谱特征离子定量分析.结果表明,填充量为0.2 g(W(活性炭)∶W(硅胶)=1∶40)的活性炭混合硅胶SPE小柱能有效地将ClPAHs分离出来,载样后采用反向溶剂洗脱,既提高了回收率又减少了洗脱剂甲苯的用量,净化效果好.处理灰尘样品后检测分析,20种ClPAHs的平均回收率稳定在60.4%—120.1%,相关系数>0.99,检出限为0.04—0.17 ng.g-1,相对标准偏差为1.6%—10.2%.本方法前处理简单,定性、定量准确可靠,可广泛应用于环境介质中氯代多环芳烃的检测.     

Electrolytic aminated carbon materials for the electrocatalytic redox reactions of inorganic and organic compounds

Some kinds of amine groups can be introduced to the glassy carbon surface by the electrode oxidation of the carbon electrode surface in ammonium carbamate solution, and this amine groups modified electrode is named as an aminated glassy carbon electrode. The existences of not only primary amine but also secondary and tertially amines were confirmed by X ray photoelectron spectroscopy. The applications of the aminated carbon material for the electrocatalytic reductions of oxygen, hydrogen peroxide, and organic compounds such as quinones were carried out, and the effects of amination on the formation of electrocatalytic sites for many species were revealed. The electrocatalyzed cyclic voltammograms of metal ions and metal chelate compounds obtained by aminated glassy carbon electrodes are also discussed. Moreover, we intend to describe that the aminated carbon electrode can exhibit the large reduction waves of inorganic oxoacids such as N0₂? or bromide ion. The introduced functional groups containing nitrogen atom can change the distribution of the electron densities of the graphite carbon surface, and this specific electron distribution environment may generate the various electrocatalytic activities.     

Resource-availability scenario analysis for formal and informal recycling of end-of-life electrical and electronic equipment in China

In strategic end-of-life electrical and electronic equipment (EoL EEE) management, it has become important to not only avoid the negative environmental impacts but also enhance the positive effects of secondary resource utilization. This is especially true in emerging countries such as China, where medium- to long-term increases in the amount of EoL EEE generation are projected. This study aims to assess the resource availability potential for EoL EEE recycling based on penetration scenarios for formal and/or informal treatment options in China. We categorized substances contained in EoL television sets and personal computers into environmental, resource, and economic aspects under consideration of product transitions. Barium and copper have a high negative potential impact on human health and/or the ecosystem. Focusing on metals with a high resource potential, the resource availability is assessed under different treatment options using characterization factors identified through a life-cycle impact assessment method, the ReCiPe 2008. The results suggest that copper and lead recycling could alleviate the increase in mining costs of resource utilization. Scenario analysis for penetration of formal and informal recycling options indicated that the difference in the alleviated mining costs between the status quo and short-term transition projections until 2030 corresponds to 2.1–2.4 billion dollars.     

Seasonal variations of water column nutrients in the inner area of Ariake Bay, Japan: the role of muddy sediments

To investigate seasonal variations of nutrient distribution in the mudflat–shallow water system, we conducted field surveys once a month from August 2007 to July 2008 in the inner area of Ariake Bay (IAB), Japan. The NH₄ ⁺–N concentration of the water column increased in autumn because of the high NH₄ ⁺ release from the sediments, ranging from 850 to 3,001 μmol?m^?2?day^?1. The NO₃ ^?–N concentration was maximal in January, which was thought to be caused by NO₃ ^? release from the oxic sediments and by NO₃ ^? regeneration due to water column nitrification. The PO₄ ^3?–P concentration of the water column was high in summer–autumn due to the high PO₄ ^3? release from the reduced sediments, ranging from 22 to 164 μmol?m^?2?day^?1. We estimated the total amounts of DIN and PO₄ ^3?–P release (R _DIN and $ {R_{{\mathrm{P}{{\mathrm{O}}_4}}}} $ , respectively) from the muddy sediment area of the IAB. In summer–autumn, R _DIN and $ {R_{{\mathrm{P}{{\mathrm{O}}_4}}}} $ corresponded to about 47.7 % of DIN input and about 116.6 % of PO₄ ^3?–P input from the river, respectively. Thus, we concluded that the muddy sediments were an important source of nutrients for the water column of the IAB during summer–autumn. In addition, we found that phosphorus necessary for the growth of Porphyra (Porphyra yezoensis, Rhodophyceae) would be insufficient in the water column when phosphorus during the Porphyra aquaculture period is supplied only from the river. Therefore, the phosphorus release from the muddy sediments was thought to play an important role in the sustainable production of Porphyra in Ariake Bay.     

Identification and characterization of coagulation inhibitor proteins derived from cyanobacterium Microcystis aeruginosa

The excess growth of cyanobacteria in semi enclosed water areas caused by eutrophication brings about coagulation inhibition in drinking water treatment processes. In this study, coagulation inhibitor proteins produced by Microcystis aeruginosa, a major cyanobacterium in algal bloom, were acquired by a phage display technique, an aluminum-immobilized affinity chromatography and a protein expression technique using Escherichia coli cells. Two cyanobacterial peptides with a high ratio of metallophilic amino acids were recovered, which were a part of homologues of a thiol oxidase enzyme Ero1p and a trans-acting repressor ArsR. It was also shown that the homologue of ArsR exhibited a stronger inhibitory effect on the coagulation of kaolin suspension with polyaluminum chloride than the control proteins. This is the first report to identify a cyanobacterial cell component to inhibit coagulation. The compositions of polar amino acids were critical to explain the strength of coagulation inhibition potential. Polar proteins from cyanobacteria could collectively consume coagulants or stabilize clay particles, which would be plausible explanations for causing coagulation inhibition. Meanwhile, results from the kaolin coagulation tests using the control proteins implied that the neutralization of positive charges of coagulant constituents by simple electrostatic interactions might not be the key mechanism on the protein-induced coagulation inhibition.     

Synthesis of novel polymer type sulfoxide solid phase combined with the porogen imprinting for enabling selective separation of polychlorinated biphenyls

We developed a novel polymer type sulfoxide-modified solid phase enabling to achieve selective separation of polychlorinated biphenyls (PCBs) from insulation oil. In this study, firstly we prepared base-polymer based on the concept of the molecular imprinting to capture PCBs in selectively, then, the sulfoxide groups were modified on the pore surface of base-polymers by changing preparation methods. As results of liquid chromatographic analyses for the polymers as columns, the base-polymer prepared by xylene as a porogenic solvent showed selective retention ability for chlorinated aromatic compounds by the porogen imprinting effect. Additionally, the polymer-type sulfoxide solid phases showed highly retention ability for PCBs by increasing amount of introduced sulfoxide groups. Consequently, the results of separation of PCBs comparing to insulation oil suggested that the prepared solid phase can be used for the selective separation of PCBs at the same level as a commercially available media utilized for the regulated method.     

Polychlorinated biphenyls and -naphthalenes in pine needles and soil from Poland--concentrations and patterns in view of long-term environmental monitoring

Pine needles were selected as cost effective and easy collectable matrices suitable for long-term monitoring of the lower troposphere pollution with polychlorinated biphenyls and polychlorinated naphthalenes. The fingerprints of PCNs and PCBs in the top layers of agricultural soils were used for determination of point sources of pollution for terrestrial ecosystems. The new idea based on the use of nona- and decachlorinated isomers fingerprint as an additional tool suitable for the identification of potential point sources of pollution with PCBs, seemed to be a capable tool to identify contamination of soil and ambient air related to former manufacturing and the use of highly chlorinated technical PCB preparations.     

Health risk assessment for polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans, and polychlorinated naphthalenes in seafood from Guangzhou and Zhoushan, China

This study determined the concentrations of organochlorine contaminants in common seafood in two Chinese coastal cities (Guangzhou and Zhoushan), and assessed the health risk due to the daily consumption of contaminated seafood. Twenty-six pooled samples, belonging to five food categories (fish, bivalves, shrimp, crab, and cephalopods), were purchased from local markets in Guangzhou and Zhoushan in 2003 and 2004. These samples were analyzed for total polychlorinated biphenyls (PCBs), non- and mono-ortho-PCBs (coplanar PCBs), polychlorinated naphthalenes (PCNs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs). The concentrations of total PCBs and coplanar PCBs in fish samples were higher in Guangzhou than in Zhoushan, while the levels of PCNs and PCDDs/DFs were comparable between the two cities. The total daily intake values of dioxin-like compounds were 1.05 and 0.86pg WHO-TEQ/kg body weight in Guangzhou and Zhoushan, respectively. Hazard ratios of non-cancer risk in the two cities were all less than unity.     

Sensitivity analysis of source regions to PM2.5 concentration at Fukue Island,Japan

The authors analyze the sensitivities of source regions in East Asia to PM_2.5 (particulate matter with an aerodynamic diameter of ≤2.5 µm) concentration at Fukue Island located in the western part of Japan by using a regional chemical transport model with emission sensitivity simulations for the year 2010. The temporal variations in PM_2.5 concentration are generally reproduced, but the absolute concentration is underestimated by the model. Chemical composition of PM_2.5 in the model is compared with filter sampling data in spring; simulated sulfate, ammonium, and elemental carbon are consistent with observations, but mass concentration of particulate organic matters is underestimated. The relative contribution from each source region shows the seasonal variation, especially in summer. The contribution from central north China (105°E–124°E, 34°N–42°N) accounts for 50–60% of PM_2.5 at Fukue Island except in summer; it significantly decreases in summer (18%). Central south China (105°E–123°E, 26°N–34°N) has the relative contribution of 15–30%. The contribution from the Korean Peninsula is estimated at about 10% except in summer. The domestic contribution accounts for about 7% in spring and autumn and increases to 19% in summer. We also estimate the relative contribution to daily average concentration in high PM_2.5 days (>35 μg m^?3). Central north China has a significant contribution of 60–70% except in summer. The relative contribution from central south China is estimated at 46% in summer and about 30% in the other seasons. The contributions from central north and south China on high PM_2.5 days are generally larger than those of their seasonal mean contributions. The domestic contribution is smaller than the seasonal mean value in every season; it is less than 10% even in summer. These model results suggest that foreign anthropogenic sources have a substantial impact on attainment of the atmospheric environmental standard of Japan at Fukue Island.

Implications: The contribution from several source regions in East Asia to PM_2.5 concentration at Fukue Island, a remote island located in the western part of Japan and close to the Asian continent, is estimated using a three-dimensional chemical transport model. The model results suggest that PM_2.5 that is attributed to foreign anthropogenic sources have a larger contribution than that of domestic pollution and have a substantial impact on attainment of the atmospheric environmental standard of Japan at Fukue Island.     

Novel evidence for natural formation of dioxins in ball clay

Elevated concentrations of dioxins in ancient ball clay from the Mississippi Embayment suggest natural formation of dioxins in the environment. Evidence for such natural formation in ball clay derives from unique congener profiles in undisturbed ancient clay deposits and from the lack of other anthropogenic contaminants. Here we present novel evidence of natural formation of dioxins based on congener-specific carbon isotopic analysis of octachlorodibenzo-p-dioxin (OCDD) in ball clays from the USA and Japan. The analyses were performed using a combination of double-column high performance liquid chromatography clean-up and two-dimensional gas chromatography-isotope ratio mass spectrometry. Elevated concentrations of OCDD found in ball clays from the USA and Japan were isotopically distinguished from the anthropogenic source materials (fly ash and pentachlorophenol) and environmental samples (sediment and soil). The isotopic signatures and the occurrence of OCDD in ancient ball clays deposited in the Tertiary Era provide evidence for the in situ formation of dioxins.