吹脱-捕集气相色谱法测定底质中易挥发性有机物

研究并建立了利用吹脱－捕集气相色谱法测定底质中易挥发性有机物的分析方法。该方法对底质中２５种易挥发性有机物进行测定。方法回收率在９６％－１０５％,最低检出浓度在０．３－１４．５μｇ／ｋｇ,变异系数在２．７％－５．３％。     

中国沿海的风暴潮灾及其防御对策

中国沿海是仅次于孟加拉湾地区的第二大风暴潮重灾区。本文分析了地质时期及历史时期我国风暴潮灾的灾害记录，揭示了中国沿海风暴潮灾的严重性，并讨论了其成因特点和成灾机理，提出了一系列防灾措施和防御对策     

海岸带风暴潮减水的统计分析

在青岛大港观测站连续30年实测资料的基础上,按照年、季、月等时段分别抽样,对风暴潮减水进行了长期统计分析.考虑到海岸地区风暴潮减水的诱因不同,在一维复合极值分布的基础上,提出了"组合分布法".新方法探讨了假设所有数据源于同一分布而产生的重现值估计误差.与年极值法和阈值法的计算结果进行了比较,说明以往算法得到的重现值偏低,并给出了青岛地区受季节变化影响的风暴减水设计重现值.统计表明,青岛大港春、秋、冬季均有风暴减水发生.由于寒潮大风是其产生的主导因素,以冬季的极值减水序列为样本,所得重现值与考虑季节变化得到的重现值相当.说明在实际工程区域,选取主要天气形势产生的水文要素为样本,替代所有观测数据,使统计计算得以简化的做法是可行的.     

Stream Temperature Surges Under Urbanization and Climate Change: Data,Models, and Responses1

ABSTRACT: Multiple anthropogenic stressors, including increased watershed imperviousness, destruction of the riparian vegetation, increased siltation, and changes in climate, will impact streams over the coming century. These stressors will alter water temperature, thus influencing ecological processes and stream biota. Quantitative tools are needed to predict the magnitude and direction of altered thermal regimes. Here, empirical relationships were derived to complement a simple model of in‐stream temperature [developed by Caissie et al. Canadian Journal of Civil Engineering 25 (1998) 250; Journal of Hydrology 251 (2001) 14], including seasonal temperature shifts linked to land use, and temperature surges linked to localized rainstorms; surges in temperature averaged about 3.5°C and dissipated over about 3 h. These temperature surges occurred frequently at the most urbanized sites (up to 10% of summer days) and could briefly increase maximum temperature by >7°C. The combination of empirical relationships and model show that headwater streams may be more pervasively impacted by urbanization than by climate change, although the two stressors reinforce each other. A profound community shift, from common cold and coolwater species to some of the many warmwater species currently present in smaller numbers, may be expected, as shown by a count of days on which temperature exceeds the “good growth” range for coldwater species.     

Current status and perspectives of accelerated carbonation processes on municipal waste combustion residues

The increasing volumes of municipal solid waste produced worldwide are encouraging the development of processes to reduce the environmental impact of this waste stream. Combustion technology can facilitate volume reduction of up to 90%, with the inorganic contaminants being captured in furnace bottom ash, and fly ash/APC residues. The disposal or reuse of these residues is however governed by the potential release of constituent contaminants into the environment. Accelerated carbonation has been shown to have a potential for improving the chemical stability and leaching behaviour of both bottom ash and fly ash/APC residues. However, the efficacy of carbonation depends on whether the method of gas application is direct or indirect. Also important are the mineralogy, chemistry and physical properties of the fresh ash, the carbonation reaction conditions such as temperature, contact time, CO₂ partial pressure and relative humidity. This paper reviews the main issues pertaining to the application of accelerated carbonation to municipal waste combustion residues to elucidate the potential benefits on the stabilization of such residues and for reducing CO₂ emissions. In particular, the modification of ash properties that occur upon carbonation and the CO₂ sequestration potential possible under different conditions are discussed. Although accelerated carbonation is a developing technology, it could be introduced in new incinerator facilities as a “finishing step” for both ash treatment and reduction of CO₂ emissions.     

Fragility assessment of bottom plates in above ground storage tanks during flood events

This study aims to improve the fundamental understanding on the performance of bottom plates in above ground storage tanks (ASTs) during flood events. To this end, fragility models that estimate the probability of material yielding and rupture in the bottom plates were derived. A significant number of ASTs are located in coastal areas and are susceptible to hurricane hazards. Consequently, ASTs have suffered severe damage during past hurricanes resulting in spills with catastrophic environmental and social impacts. Therefore, several failure modes such as flotation, buckling, and sliding have been studied in past research. However, the literature lacks studies that consider the failure of bottom plate due to uplift pressure generated during floods and there are no design guidelines to address this issue. To address this gap, fragility functions that provide the probability of failure as a function of tank geometry, material properties, design parameters, and hazard conditions were developed herein. For this purpose, Latin Hypercube Sampling was performed to span the space of these parameters uniformly. For each parameter combination, maximum stresses in bottom plates were determined using analytical formulations for simply supported and clamped boundary conditions and were compared against two different failure thresholds. The results were used to develop a closed form fragility model using step wise logistic regression. Fragility functions were applied to four case study tanks. Sensitivity analysis were performed to understand the impacts of different probability density functions for various variables on the bottom plates’ fragility. The results provided several insights such as ASTs with larger diameter were vulnerable to bottom plate failure. Comparison with other failure modes revealed that the probability of bottom plate failure was higher than flotation failure for anchored ASTs with clamped boundary condition.     

Effects of water washing on removing organic residues in bottom ashes of municipal solid waste incinerators

Due to their potential toxicity and odourous nature, the residual organics in municipal solid waste incinerators are recently gaining attention as an important issue of resources recovery apart from their complex mixture of organic counterpart. Studies of the organic fractions in municipal solid waste incinerator residues have been limited. In this study, extended solid-phase extraction of the water-washed bottom ash and liquid-phase extraction of the washing water were carried out with regard to bottom ash samples from three mass-burning incinerators in Taipei County (Taiwan) during four consecutive seasons of year 2008-2009. Supercritical fluid extraction and Soxtec extraction techniques along with GC-MS were successfully used to characterize the residual organics in weathered and washed bottom ashes. Supercritical fluid extraction provided the quantification of aliphatics and aromatic compounds such as hexanoic acid and benzaldehyde, respectively. Soxtec extraction was useful for qualitative analysis of aromatic and aliphatic groups in the ashes and many of which were odourous and toxic compounds. By mixing one unit weight (g) bottom ash with two unit volume (mL) water for 15 min, total organic carbon in the bottom ash was greatly reduced (e.g., from 4.1 to 1.8 wt.%). Among the removed were foul odour-causing compounds such as pyridine and quinoline derivatives, while some aromatic compounds such as 4-hydroxybenzaldehyde and low-molecular-weight aliphatics such as hexanoic acid remained. The results here suggest that washing with water can be an effective pre-treatment step for removing odour-causing and environmental concerned organics.     

Distribution of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in municipal solid waste incinerators

The stack flue gases and the ashes in different units of two municipal solid waste incinerators (MSWIs) are sampled to investigate the characteristics of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Bottom ashes (BA) exhibited much higher PBDD/F (8.11-52.2 pg TEQ/g) and PBDE contents (20.4-186 ng/g) than those of fly ashes (0.0932-2.02 pg TEQ/g and 0.332-25.5 ng/g), revealing that the PBDD/Fs and PBDEs in the feeding waste may not be completely destroyed. The PBDE concentrations/contents in the stack flue gases (26.1-109 ng/Nm³) and in the BA (20.4-186 ng/g) of the MSWIs could reach three orders higher than those in the atmosphere and reference soils. PBDE contributions to the environment from the stack flue gases or the reutilization of BA of MSWIs should not be ignored from the developing PBDE inventory.     

Sulfur organic compounds in bottom sediments of the eastern Gulf of Finland

Background, Aims and Scope Despite the large number of studies on the forms of sulfur in marine deposits, investigations on sulfur organic compounds are still rare. It is known that the processes leading to formation of intermediate and final sulfur compounds (including organic ones) in modern deposits are the results of microbiological transformation of sulfur containing proteins, as well as the microbiological reduction of sulfate ions. The latter are finally reduced by anaerobic sulfate-reducing bacteria to H₂S, HS⁻ and S²⁻; the total sum of these is referred to as ‘hydrogen sulfide’ in chemical oceanography. Further, the formation of reduced sulfur organic derivatives (sulfides and polysulfides) is the result of interaction of the organic substance destruction products with the sulfide ions. In such cases, the main source of organic substances, as well as sulfates for the sulfur reducing processes, is the pore water in the sediments. The choice of the target of our study is based on the fact that the eastern part of the Gulf of Finland water area receives the bulk of the anthropogenic load of the St. Petersburg region. Low vertical intermixing of the water thickness is observed there (thus creating a deficiency of oxygen near the bottom), and the bottom sea current transfers the polluted salty water of the Baltic Sea into the Neva Bay. The whole of the above are the preconditions for the formation of sulfur-bearing organic compounds. A great number of bottom sediment samples for analytical surveys were collected in the Eastern Gulf of Finland during research expeditions in the years of 1997 and 2001. These were screened for structures of sulfur organic microcontaminants, including organic forms of sulfur, using advanced instrumentation and experienced personnel in our two, cooperating laboratories. This work is a part of the research being carried out on organic micro-admixtures present in bottom sediments, and is the summary of our findings on previously unstudied sulfur organic substances there. Materials and Methods A number of sulfur organic compounds present in nineteen bottom sediment samples from the Eastern Gulf of Finland (EGF) were characterized by high performance gas chromatography connected to low and high resolution mass spectrometers (GC/LRMS and GC/HRMS). The structure screening was carried out as compared with literature and library mass spectra, and taking the GC retention times into account. In the cases of an absence of mass spectra not in the literature, interpretation of the most probable structures was performed with the help of high resolution mass-spectrometric data, fragmentation rules for sulfur-bearing organic substances and ICLU simulation of spectra. These data were registered to form a conclusive ‘fingerprint’ for identification and confirmation of the structure of each novel compound found, e.g. by later syntheses of authentic model compounds. The relative contents of sulfur organic compounds were determined from MS response ratios of each compound to 2-fluorine naphthalene (internal standard). Results This paper is a completion of work, which has been published in part as three papers in the European Journal of Mass Spectrometry. As the total study result, 43 sulfur-bearing compounds were characterized. The mass spectra of 20 of them were found in the literature. The most probable structures for the 23 compounds whose mass-spectra were not available in the literature data were proposed. All of those 23 compounds were detected in bottom sediments for the first time, and 5 of them were described as originating from plants or being generated by chemical synthesis products, while the remaining 18 substances were previously unknown. The structures of these were deduced to be most probably the following (in order of their GC retention): dichloromethyl thiylsulfenylchloride, chloromethyl dichloromethyl disulfide, 3,4-dithiacyclohexene, 1,2,4-trithiacycloheptane, 1,2,3-trithiacyclohexane, tetrathiacyclopentane, 3,4,5-trithiacyclohexene, 1,2,4-trithiacyclohexane, cyclopropylhydrotrisulfide, 1,2-dithiane-3-thiol, 1,3-dithiane-2-thiol, bis(trichloromethyl)-tri-sulfide, 1,2,4,5-tetrathiacyclohexane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathia-cyclo-hexane, pentathiacyclohexane, and 1,2,4,6-tetrathiacyclooctane. The highest amounts of sulfur organic compounds were found in the deepest, bottom areas in the open part of the sea, where the salinity was highest, and oxygen deficiency occurred as well. Also, some coastal places with a high solid matter deposition rate had elevated contents of sulfur organic compounds. Discussion From the 43 sulfur organic compounds found, the HRMS data provided the atomic composition of the molecular ions for 16 compounds with a high confidence (see Table 3). The LRMS spectra could be identified with catalogue or literature spectra in 29 cases. The MS information obtained was insufficient in two cases: 1) The obvious molecular ion (at m/z 110) of compound 1 was not visible in LRMS. 2) For compound 43, the HRMS measurement, due to the low intensity (2%) of the molecular ion (m/z 210), could not exclude the presence of 2 oxygen atoms (instead of one sulfur atom) in the molecule. Major fragments, however, of our 43, certainly contained no oxygen atoms according to HRMS. The limited LRMS data in the literature, for an isomer of 43, had m/z values of all fragments different from those of the compound found by us. The retention times (RT) formed one more evidence for identity between compounds in different samples. The use of different non-polar columns in GC and similar, but not identical, temperature programs produced eluted peaks of novel and known compounds in each sample (mixture) in GC/HRMS and GC/LRMS. These gave sets of RTs which were in a very significant linear correlation (measured example R = 0.999866, p = 1.85E-06, N = 5). Therefore, the RTs in the HRMS analysis systems could be converted to values comparable with those from the LRMS device. The RT values, HRMS m/z values, LRMS spectra, and ICLU simulation results for each organic sulfur compound form an identification ‘fingerprint’. The interpretation of these experimental data, with supporting use of fragmentation rules, allow the giving of a provisional name and structure to the ‘suspect’. In this study and in environmental surveys of micropollutants in general, the compounds suspected of anthropogenic or natural origin occur at low levels in complex mixtures. Therefore, no bulk amount of an authentic, pure model substance for the suspect is available quite often. The most probable name and structure from the fingerprint data are very useful in guiding the preparation of the model substance for a conclusive identification. Similarly, the unknown criminal can be identified in advance by forensic science and his fingerprint, DNA, etc. as registered before the arrest. The analogy can be found in the literature and CAS register of organic polysulfides, which in great part consists of the results of sensitive mixture analysis methods. Conclusions Sediment of the Eastern Gulf of Finland is over large areas anaerobic, as indicated by the existence of novel, non-oxygenated sulfur organic microcontaminants. These substances were most abundant in anoxic and saline, deep bottom regions, and, in addition, in one coastal area near industrial discharges. This occurrence, and also the limited information about sulfur organic compounds in scientific literature, is considered evidence for the dominantly natural processes in their formation. Recommendations and Perspectives The importance and necessity of investigating the sulfur organic compounds in the bottom sediments, result from the fact that their presence can be an indicator of stable anaerobic processes. Similarly, the oxygen disappearance (anoxia) in the marine water, due to a high concentration of the sulfate ions and relatively high content of organic matter, is practically always connected with the appearance of hydrogen sulfide and sulfides. The generation of sulfur organic compounds precedes the formation of the new, or expansion of the existing anaerobic (‘hydrogen sulfide’) zones, which lead to such environmental disasters as mass destruction of hydrobionts. Many organic compounds of sulfur, including sulfides and polysulfides, are toxic to the aquatic organisms. Therefore, in addition to the danger of mass wholesale deaths of marine fauna in the bottom sediments region, there exists a probability of secondary pollution of the water thickness as well, due to the entry of those substances from bottom sediments in the water when the environmental conditions are changed (stormy weather, floods, geological activity of the earth’s crust, etc.).     

广东沿海风暴潮灾害应急管理初探

广东沿海由于特殊的地理位置和气候条件,是风暴潮灾害的高发区。在分析广东沿海风暴潮灾害特点、广东省风暴潮灾害防御体系建设现状的基础上,总结了广东沿海风暴潮灾害应急管理中存在的问题,并提出了相应的对策和建议,可供工程技术人员和政府管理人员参考。