气袋采样法对还原硫化物测定的影响因素分析及机理研究

还原硫化物是一Z类典型的恶臭物质,其特点是活性高、不易储存,因此适宜的储存条件对还原硫化物的准确测定具有重要意义。本文使用气相色谱-质谱联用技术,从气袋材质、还原硫化物初始浓度、还原硫化物性质和储存时间四个因素探究袋采样法储存还原硫化物过程的损失情况。以Tedlar~? PVF和Teflon~? FEP为目标采样袋,使用5个初始浓度(0. 001、0. 010、0. 100、1. 000和10. 000μg/m L)的混合还原硫化物,选择0、2、6、12、24、48以及72h的储存时间,以响应因子和相对回收率作为评价因子,并使用配对t检验法和吸附动力学,研究影响储存效果的主要因素、物质损失机理以及两种采样袋的储存能力。结果表明,储存时间越长、物质初始浓度越高,物质活性越强,损失情况越严重;在环境温度达到60℃时,Tedlar~? PVF的基质背景较Teflon~? FEP更复杂;相同条件下,还原硫化物在Teflon~? FEP储存过程中损失更严重。依据研究结果建议:(1)样品采集后避光保存;(2)低浓度含硫样品的测定在采样后8h内完成,高浓度含硫样品的测定在2h内完成;(3)若待测样品气体温度较高,优先选择Teflon~? FEP采样袋,气体温度较低条件下选择Tedlar~? PVF采样袋,可最大限度保持样品的原始状态。本研究成果有利于确保还原硫化物样品的储存稳定性,最大限度还原恶臭污染现场情况,为恶臭污染的分析测试以及后续的恶臭污染控制与治理提供技术支持。     

原子荧光光谱测定土壤和水系沉积物中硒的干扰来源及消除方法

原子荧光光谱法(AFS)具有灵敏度高、结构简单、容易操作等优点,但目前测定土壤和沉积物中的硒等元素的标准方法所采用的消解过程繁琐,易产生干扰。沸水浴可以把土壤和水系沉积物中硒提取完全,本文根据样品中元素丰度和仪器性能,将AFS测定Se的干扰分为Cu和Pb两大类,根据实验提出在水浴消解液加入浓盐酸(不宜加入硫脲-抗坏血酸),通过增加溶液酸度和Cl~-浓度,即保持样品中盐酸浓度高于23%,可抑制Cu~(2+)还原为Cu~0和Pb~(4+)生成PbH_4,有效降低了Cu的负干扰和Pb的正干扰,提高了AFS测定Se的精密度和准确度。本方法测定Se的检出限为0.008mg/kg,测试标准物质的相对标准偏差为0.5%～11%,相对误差为-16.3%～9.5%;比行业标准HJ 680—2013的检出限(0.01mg/kg)、精密度(0.79%～23.1%)和准确度等技术指标更佳。     

Dynamic soil–structure interaction analysis via coupled finite-element–boundary-element method

In this paper, a study on the transient response of an elastic structure embedded in a homogeneous, isotropic and linearly elastic half-plane is presented. Transient dynamic and seismic forces are considered in the analysis. The numerical method employed is the coupled Finite-Element–Boundary-Element technique (FE–BE). The finite element method (FEM) is used for discretization of the near field and the boundary element method (BEM) is employed to model the semi-infinite far field. These two methods are coupled through equilibrium and compatibility conditions at the soil–structure interface. Effects of non-zero initial conditions due to the pre-dynamic loads and/or self-weight of the structure are included in the transient boundary element formulation. Hence, it is possible to analyse practical cases (such as dam–foundation systems) involving initial conditions due to the pre-seismic loads such as water pressure and self-weight of the dam. As an application of the proposed formulation, a gravity dam has been analysed and the results for different foundation stiffness are presented. The results of the analysis indicate the importance of including the foundation stiffness and thus the dam–foundation interaction.     

Characterisation of Fulvic Acids and Glycyrrhizic Acid by Time‐of‐Flight Secondary Ion Mass Spectrometry

Fulvic acids of different origin, spray deposited on polished silicon after dissolution in high‐purity water without any additives, were analysed by time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) in combination with oblique 24...36 keV SF₅⁺ ion bombardment. The observed, highly reproducible mass spectra cover more than five orders of magnitude in dynamic range, without background subtraction. Apart from lines due to atomic ions and low‐mass ion fragments, the mass spectra exhibit broad maxima between m/z 200...350, mainly due to a beat‐like superposition of lines at every single mass number, up to at least m/z 400. In the negative ion spectra the beats have a spacing of m/z 14, corresponding to a CH₂‐unit. The high‐mass tails of the spectra extend well beyond m/z 5000, with similar slopes in the positive and the negative ion mass spectra. The negative spectra appear to be less affected by fragmentation products than the positive spectra. Fulvic acids (FAs) of different origin show distinctly different spectra, with mean masses ranging between m/z ≈ 450 and 580 (for a low‐mass cut‐off m/z 150). To further verify the ability of TOF‐SIMS to detect molecules and clusters with masses significantly above the maxima of the FA spectra, samples of glycyrrhizic acid (GA, as GA ammonium salt with molecular weight 840) were also analysed. Parent ions as well as multimers (GA)_n were observed as positive and negative ions, up to n = 4 (m/z 3320). The results are compared with spectra recently obtained by other mass spectrometric techniques.     

Subaquatic slope instabilities: The aftermath of river correction and artificial dumps in Lake Biel (Switzerland)

River engineering projects are developing rapidly across the globe, drastically modifying water courses and sediment transfer. Investigation of the impact of engineering works focuses usually on short-term impacts, thus a longer-term perspective is still missing on the effects that such projects have. The ‘Jura Water Corrections’ – the largest river engineering project ever undertaken in Switzerland – radically modified the hydrological system of Lake Biel in the 19th and 20th Century. The deviation of the Aare River into Lake Biel more than 140 years ago, in 1878, thus represents an ideal case study to investigate the long-term sedimentological impacts of such large-scale river rerouting. Sediment cores, along with new high-resolution bathymetric and seismic reflection datasets were acquired in Lake Biel to document the consequences of the Jura Water Corrections on the sedimentation history of Lake Biel. Numerous subaquatic mass transport structures were detected on all of the slopes of the lake. Notably, a relatively large mass transport complex (0·86 km²) was observed on the eastern shore, along the path of the Aare River intrusion. The large amount of sediment delivered by the Aare River since its deviation into the lake likely caused sediment overloading resulting in subaquatic mass transport. Alternatively, the dumping since 1963 in a subaquatic landfill of material excavated during the second phase of river engineering, when the channels flowing into and out of Lake Biel were widened and deepened, might have triggered the largest mass transport, dated to 1964 or 1965. Additional potential triggers include two nearby small earthquakes in 1964 and 1965 (M_W 3·9 and 3·2, respectively). The data for this study indicate that relatively large mass transports have become recurrent in Lake Biel following the deviation of the Aare River, thus modifying hazard frequency for the neighbouring communities and infrastructure.     

Coherence algorithm with a high-resolution time–time transform and feature matrix for seismic data

Traditional coherence algorithms are often based on the assumption that seismic traces are stationary and Gaussian. However, seismic traces are actually non-stationary and non-Gaussian. A constant time window and the canonical correlation analysis in traditional coherence algorithms are not optimal for non-stationary seismic traces and cannot describe the similarity between adjacent seismic traces in detail. To overcome this problem, a new coherence algorithm using the high-resolution time–time transform and the feature matrix is designed. The high-resolution time–time transform used to replace the constant time window can produce a frequency-dependent time local series to analyse non-stationary seismic traces. The feature matrix, constructed by the frequency-dependent time local series and the related local gradients, defines a new correlation metric that enhances more details of the geological discontinuities in seismic images than does the canonical correlation analysis. Additionally, the Riemannian metric is introduced for related calculations because the feature matrices are not defined in a Euclidean space but rather in a manifold space. Application to field data illustrates that the proposed method reveals more details of structural and stratigraphic features.     

Untersuchungen zum Abbau von Pharmaka in kommunalen Kläranlagen mit HPLC-Electrospray-Massenspektrometrie

Examination of the Degradation of Drugs in Municipal Sewage Plants Using Liquid Chromatography-Electrospray Mass Spectrometry Numerous drugs can be identified in the secondary effluent of municipal sewage plants. In order to obtain information about the degree of elimination (adsorption, aerobic degradation) of these compounds, a batch reactor containing different drugs in environmentally relevant concentrations and a suspension of activated sludge was coupled to a HPLC-MS-MS system. During a testing period of three days concentration-time-curves were recorded. For most of the examined drugs (acetamidoantipyrine, crotamiton, diclofenac, primidone, propyphenazone) solely a strong decrease of the initial concentration within the first 15 minutes was observed, which was interpreted primarily as adsorption to the activated sludge. For acetaminophenol and pentoxifyllin an additional slower decrease in concentration within several hours was observed. This slower elimination was interpreted to be caused mainly by primary degradation. It could be shown that dihydrocodeine is oxidized to hydrocodone in the batch reactor. The conjugate acetaminophen glucuronide was cleaved.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part III: Determination of Synthetic Musks in Berlin Surface Water Applying Solid-phase Microextraction (SPME) and Gas Chromatography-Mass Spectrometry (GC-MS)

Polycyclic musks and nitro musks were found as environmental pollutants in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. These synthetic musks, which are used as fragrances in cosmetics, detergents, and other products, are discharged by the municipal sewage treatment plants into Berlinπs surface waters. In particular, the polycyclic musks 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyrane (HHCB; Galaxolide®, Abbalide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetraline (AHTN; Tonalide®, Fixolide®) were found in the receiving surface waters at considerable concentrations up to the μg/L-level. In the Wuhle, a small brook almost totally consisting of sewage effluents, maximum concentrations were 12.5 μg/L for HHCB and 6.8 μg/L for AHTN. Additionally, the polycyclic musk 4-acetyl-1,1-dimethyl-6-tert-butylindane (ADBI; Celestolide®, Crysolide®) and 1-tert-butyl-3,5-dimethyl-2,6-dinitro-4-acetylbenzene (musk ketone) were detected at low concentrations in most of the samples. Two other nitro musks, namely 1,1,3,3,5-pentamethyl-4,6-dinitroindene (musk moskene) and 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene), were only detected in a single surface water sample. Solid-phase microextraction (SPME) with detection by gas chromatography-mass spectrometry (GC-MS) has proven to be a rapid and reliable tool for the screening of synthetic musks in surface and sewage water samples. Internal calibration with a suitable internal standard enables reproducible quantitation of the analytes down to the low ng/L-level.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin.Part II: Substituted Phenols in Berlin Surface Water

In a surface water screening, 30 representative surface water samples collected from rivers, canals, and lakes in Berlin were investigated for the presence of 22 substituted phenols. The phenols selected include the 11 phenols considered as “priority pollutants” by the US Environmental Protection Agency (US-EPA). Surface water samples were extracted applying solid-phase extraction with styrenedivinylbenzene adsorbent. The recoveries, determined in spiking experiments, were between 80 % and 103 %. After derivatization with N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) the samples were analyzed by capillary gas chromatography-mass spectrometry (GC-MS). Phenol, cresols, 2-ethylphenol, 2-chlorophenol, 4-chloro-3-methylphenol, pentachlorophenol, 2-nitrophenol, and 4-nitrophenol were detected in the surface water samples at concentrations between 0.02 μg/L and 7.8 μg/L, respectively. The distribution of these residues in the Berlin surface waters showed that the phenolic residues, with the exception of pentachlorophenol and 2-ethylphenol, do not originate primarily from municipal sewage treatment plants discharges. Some of the phenols are formed naturally or occur as ubiquitous anthropogenic contaminants in the aquatic system.     

High-resolution sequence stratigraphy,sedimentology and reservoir quality evaluation of the Yaojia Formation in the Longxi area of the Western Slope,Songliao Basin,China

Delta-front sand bodies with large remaining hydrocarbon reserves are widespread in the Upper Cretaceous Yaojia Formation in the Longxi area of the Western Slope, Songliao Basin, China. High-resolution sequence stratigraphy and sedimentology are performed based on core observations, well logs, and seismic profile interpretations. An evaluation of the reservoir quality of the Yaojia Formation is critical for further petroleum exploration and development. The Yaojia Formation is interpreted as a third-order sequence, comprising a transgressive systems tract (TST) and a regressive systems tract (RST), which spans 4.5 Myr during the Late Cretaceous. Within this third-order sequence, nine fourth-order sequences (FS9–FS1) are recognized. The average duration of a fourth-order sequence is approximately 0.5 Myr. The TST (FS9–FS5) mostly comprises subaqueous distributary channel fills, mouth bars, and distal bars, which pass upward into shallow-lake facies of the TST top (FS5). The RST (FS4–FS1) mainly contains subaqueous distributary-channel and interdistributary-bay deposits. Based on thin-sections, X-ray diffraction (XRD), scanning electron microscope (SEM) and high-pressure mercury-intrusion (HPMI) analyses, a petrographic study is conducted to explore the impact of the sedimentary cyclicity and facies changes on reservoir quality. The Yaojia sandstones are mainly composed of lithic arkoses and feldspathic litharenites. The sandstone cements mostly include calcite, illite, chlorite, and secondary quartz, occurring as grain coating or filling pores. The Yaojia sandstones have average core plug porosity of 18.55% and permeability of 100.77 × 10⁻³ μm², which results from abundant intergranular pores and dissolved pores with good connectivity. Due to the relatively coarser sediments and abundant dissolved pores in the feldspars, the FS4–FS1 sandstones have better reservoir quality than the FS9–FS5 sandstones, developing relatively higher porosity and permeability, especially the FS1 and FS2 sandstones. The source–reservoir–cap-rock assemblages were formed with the adjoining semi-deep lake mudstones that were developed in the Nenjiang and Qingshankou Formations. This study reveals the deposition and distribution of the delta-front sand bodies of the Yaojia Formation within a sequence stratigraphic framework as well as the factors controlling the Yaojia sandstones reservoir quality. The research is of great significance for the further exploration of the Yaojia Formation in the Longxi area, as well as in other similar lacustrine contexts.