Bestimmung polarer Phosphorsäureester in Trink‐ und Oberflächenwasser mittels HPLC‐MS‐MS

Determination of Organophosphorus Pesticides in Water by HPLC‐MS‐MS In the EC Water Framework Directive 2000/60/EG and in CEC 76/464/EEC there are 16 organophosphorus pesticides (insecticides and acaricides) listed which belong to so‐called priority substances. The committed quality aims of these substances frequently require maximum concentrations below 0.1 μg/L. In this paper a HPLC‐MS‐method is described. The reported limits of determination of organophosphorus pesticides are lower than the demanded limits. High analytical sensitivity is reached by solid‐phase extraction (SPE) and by injecting large volumes. For some of these substances no sample enrichment is needed and low detection limits are obtained by direct injection of the original water sample.     

Verringerung der Schwermetall‐ und Sulfatbelastung in sauren bergbaubelasteten Gewässern durch Aluminiumpräzipitate

Attenuation of Heavy Metals and Sulfate by Aluminium Precipitates in Acid Mine Drainage During the mixing of acid mine waters with nearly neutral tributaries, often precipitates are formed which are high in iron or aluminium. These precipitates cover the river bed for many kilometres. Near the town of Lehesten (Thuringian slate mining area), leachates of slate quarries and waste rock dumps contain high amounts of aluminium, sulfate, copper, nickel, zinc, manganese, and H⁺ ions as a result of the oxidation of incorporated pyrite. These leachates enter the brooks Loquitz, Kleine Sormitz, and Rehbach leading to the phenomenon named above. The contribution of the forming aluminium‐rich precipitates on the attenuation of sulfate and heavy metals by sorption or coprecipitation was studied by analysing the composition of water and sediment samples as well as samples of suspended matter. Sulfate is often considered as conservative tracer in acid mine drainage. However, sulfate does not behave conservatively in this system what might be explained by the adsorption of sulfate to the aluminium precipitates. Instead, conservative behaviour was found for calcium, potassium, chloride, zinc, manganese, and nickel. A formation of jurbanite can be excluded because of the low sulfate contents. The sulfate content of the sediment depends on the pH. At low pH values (4.8) the S/Al ratio corresponds to the theoretical ratio in basaluminite and decreases with rising pH. Sulfate is weakly bound to the solid phase and can easily be replaced by OH^– ions. A formation of basaluminite is possible at low pH values with a fluent transition to aluminium hydroxide. Therefore the precipitates are assumed to consist predominantly of aluminium hydroxide with sulfate being adsorbed to the surface.     

Die neue EG‐Wasserrahmenrichtlinie: Bewertung der chemischen und ökologischen Qualität von Oberflächengewässern

The New EC Framework Water Directive: Assessment of the Chemical and Ecological Status of Surface Waters The main objective of the draft EC Framework Water Directive is the good quality of all surface waters. The directive provides for an assessment of the chemical status of surface waters (EU‐wide valid environmental quality standards for approximately 30 priority substances) and a five‐stage ecological classification of waters, comprising the stages high, good, moderate, poor, and bad. The starting point for the assessment are the reference conditions, which are defined as corresponding to high water quality and characterising a water status with no significant anthropogenic impact. The reference sites in the various water body types are to be selected using hydromorphological and physico‐chemical parameters and subsequently characterised by means of biological parameters. For surface waters, three groups of characteristics are provided for, namely: 1. with priority the biology – in the case of surface waters – with the four elements phytoplankton, macrophytes/phytobenthos, benthic invertebrate fauna, and fish fauna; 2. supporting the hydromorphology, e.g. flowing waters with the three elements hydrological regime, river continuity, and morphological conditions and 3. supporting the physico‐chemical conditions with the three elements general conditions, specific synthetic pollutants, and specific non synthetic pollutants (other than the priority substances of the chemical status).     

Die EG‐Wasserrahmenrichtlinie: Ausweisung und Bewertung künstlicher und erheblich veränderter Gewässer

Designation and Assessment of Artificial and Heavily Modified Water Bodies under the EC Water Framework Directive The EC Water Framework Directive allows the Member States to designate artificial and heavily modified water bodies under specific conditions. For those water bodies the ecological assessment and the resulting programmes of measures will be based on the “maximum ecological potential” as reference conditions and not on the “high ecological status”, which has to be used for natural water bodies. Such designation is possible only, if the hydromorphology of the water bodies concerned has been substantially changed in character to maintain specified uses. The criteria for the designation are fulfilled, if restoration measures needed to meet the high ecological status would have significant adverse effects on the uses and if no other better environmental options would exist to maintain the specified uses. In late 1999 the EC‐Working Group on Heavily Modified Water Bodies (HMWB) has been established to develop criteria for the designation of artificial and heavily modified water bodies as well as for the determination of the maximum ecological potential. The working group has produced the guidance document “Identification and Designation of Artificial and Heavily Modified Water Bodies” in November 2002, which has been agreed by the European Water Directors on 21 November 2002 in Copenhagen. The guidance document is focusing on two time borders, the provisional identification of heavily modified water bodies until 2004 and the legally binding designation as artificial and heavily modified in the first river basin management plan in 2009 at the latest. The guidance document considered the main findings of 34 case studies for rivers, lakes, transitional and coastal waters carried out in 11 European countries. The results of the case studies as well as a summarizing synthesis were used as a fundamental basis to produce the guidance document. The practical examples given by the case studies were compiled as a toolbox which supplements the guidance for the purpose of its better application.     

Novel Calix[4]arene‐based Amberlite XAD‐4 Modified Resin for As(III) Removal from Water

The present article describes As(III) sorption behavior of novel calix[4]arene appended TS‐4 resin. The sorption ability of TS‐4 resin has been evaluated at wide range of pH, i.e., pH 2–14. The maximum As(III) sorption efficiency (95%) was achieved at pH 2, which shows that the TS‐4 resin possesses greater affinity for As(III) at this pH. Column sorption mechanism was evaluated through various operating parameters, i.e., change in concentration, flow rate, bed heights, and pH. The experimental data were also tested against bed depth service time model and from the results; it has been observed that the data is in close agreement with the theoretically calculated values. Thus, from the data it has been revealed that TS‐4 resin has maximum column efficiency of 0.13 mmol g^?1. Application of TS‐4 to real samples indicates a slight decrease (2–3%) in extraction efficiency of TS‐4 because of high concentration of total dissolved salts. Thermal behavior was tested by differential scanning calorimetry and it has been observed that TS‐4 resin is stable up to 160°C. TS‐4 resin was found to be regenerable and best regeneration was achieved by using 4% solution of NaOH. It can be deduced from the study that the resin will find its applicability in small as well as industrial scale water purification plants.     

Influence of Surfactants on Degradation of 1‐(2‐Chlorobenzoyl)‐3‐(4‐chlorophenyl) Urea by Nanoscale Zerovalent Iron

Nanoscale zerovalent iron (NZVI) has been proved to be effective in the degradation of environmental pollutants and exhibits advantages in the removal of 1‐(2‐chlorobenzoyl)‐3‐(4‐chlorophenyl) urea (CCU), an analog of diflubenzuron. This present study focused on the influence of surfactants in the degradation procedure with NZVI in order to provide a simple and rapid removal method for CCU. Triton X‐100, Tween 20, Tween 80, sodium dodecyl sulfonate (SDS), and cetyltrimethylammonium bromide (CTAB) were investigated under anaerobic conditions. The experimental results demonstrated that the degradation rate increased sharply with the presence of SD during the first 15 min, up to 99.97% with addition of 0.01 g L^?1 SDS, whereas the presence of Triton X‐100, Tween 80, and Tween 20 resulted in a slight enhancement of the degradation of CCU. The enhancement strength of them was in the order Tween 20, Triton X‐100, and Tween 80. However, addition of the cationic surfactant CTAB resulted in a significant inhibitive effect. In contrast, the mixed surfactants did not result in the expected performance, and the performance was lower than that using some certain single surfactant among the mixed surfactants.     

Sulfur and carbon isotopic systematics of Guadalupian‐Lopingian (Permian) mid‐Panthalassa: δ34S and δ13C profiles in accreted paleo‐atoll carbonates in Japan

Immediately before the extinction of the end‐Guadalupian (Middle Permian; ca 260 Ma), a significant change to the global carbon cycle occurred in the superocean Panthalassa, as indicated by a prominent positive δ¹³C excursion called the Kamura event. However, the causes of this event and its connection to the major extinction of marine invertebrates remain unclear. To understand the mutual relationships between these changes, we analyzed the sulfur isotope ratio of the carbonate‐associated sulfate (CAS) and HCl‐insoluble residue, as well as the carbon isotope ratio of bulk organic matter, for the Middle‐Upper Permian carbonates of an accreted mid‐oceanic paleo‐atoll complex from Japan, where the Kamura event was first documented. We detected the following unique aspects of the stable carbon and sulfur isotope records. First, the extremely high δ¹³C values of carbonate (δ¹³C_carb) over +5 ‰ during the Capitanian (late Guadalupian) were associated with large isotopic differences between carbonate and organic matter (Δ¹³C = δ¹³C_carb ? δ¹³C_org). We infer that the Capitanian Kamura event reflected an unusually large amount of dissolved organic matter in the expanded oxygen minimum zone at mid‐depth. Second, the δ³⁴S values of CAS (δ³⁴S_CAS) were inversely correlated with the δ¹³C_carb values during the Capitanian to early Wuchiapingian (early Late Permian) interval. The Capitanian trend may have appeared under increased oceanic sulfate conditions, which were accelerated by intense volcanic outgassing. Bacterial sulfate reduction with increased sulfate concentrations in seawater may have stimulated the production of pyrite that may have incorporated iron in pre‐existing iron hydroxide/oxide. This stimulated phosphorus release, which enhanced organic matter production and resulted in high δ¹³C_carb. Low δ³⁴S_CAS values under high sulfate concentrations were maintained and the continuous supply of sulfate cannot by explained only by the volcanic eruption of the Emeishan Trap, which has been proposed as a cause of the extinction. The Wuchiapingian δ³⁴S_CAS–δ¹³C_carb correlation, likely related to low sulfate concentration, may have been caused by the removal of oceanic sulfate through the massive evaporite deposition.     

Degradation of Disperse Blue E‐4R in Aqueous Solution by Zero‐Valent Iron/Ozone

Degradation of an anthraquinone dye, disperse blue E‐4R, by zero‐valent iron (ZVI)/ozone (O₃) was carried out in a series of laboratory‐scale experiments. The obtained results indicated that this method was much more effective than single ZVI or single O₃ at removal of color, chemical oxygen demand, total organic carbon, and adsorbable organic halogen. The effect of several related operational parameters, including O₃ dosage, zero valent iron dosage, temperature, pH value, and ZVI particle size were also discussed. Finally, we tried to decontaminate some actual samples with this method, which showed high treatment efficiency to the sample pretreated by conventional activated sludge.     

Non‐linear‐Maxwell‐element‐type hysteretic control force

A simple non‐linear control law is proposed for reducing structural responses against seismic excitations. This law defines control force dynamics by one differential equation involving a non‐linear term that restrains the control force amplitude. If non‐linearity is neglected, the control force becomes the force in a Maxwell element, so it is called the non‐linear‐Maxwell‐element‐type (NMW) control force. The NMW control force vs. deformation relation plots hysteretic curves. The basic performance of an SDOF model with the NMW control force is examined for various conditions by numerical analyses. Furthermore, the control law is extended to fit an MDOF structural model, and an application example is shown. The computational results show that the NMW control force efficiently reduces structural responses. Copyright © 2000 John Wiley & Sons, Ltd.     

Verification of system identification utilizing shaking table tests of a full‐scale 4‐story steel building

This paper verifies the feasibility of the proposed system identification methods by utilizing shaking table tests of a full‐scale four‐story steel building at E‐Defense in Japan. The natural frequencies, damping ratios and modal shapes are evaluated by single‐input‐four‐output ARX models. These modal parameters are prepared to identify the mass, damping and stiffness matrices when the objective structure is modelled as a four degrees of freedom (4DOF) linear shear building in each horizontal direction. The nonlinearity in stiffness is expressed as a Bouc–Wen hysteretic system when it is modelled as a 4DOF nonlinear shear building. The identified hysteretic curves of all stories are compared to the corresponding experimental results. The simple damage detection is implemented using single‐input‐single‐output ARX models, which require only two measurements in each horizontal direction. The modal parameters are equivalent‐linearly evaluated by the recursive Least Squares Method with a forgetting factor. When the structure is damaged, its natural frequencies decrease, and the corresponding damping ratios increase. The fluctuation of the identified modal properties is the indirect information for damage detection of the structure. Copyright © 2015 John Wiley & Sons, Ltd.     

Qualitätsanforderungen an Oberflächengewässer: Zielvorgaben,Qualitätsziele und chemische Gewässergüteklassifizierung

Quality Requirements for Fresh Waters: Water Quality Targets, Water Quality Objectives, and Chemical Water Quality Classification In the Federal Republic of Germany, water quality requirements for the protection of inland surface waters against hazardous substances are formulated on the basis of a quality targets derivation concept developed jointly by the Federal Government and the Federal States. The quality requirements were termed “water quality targets” in order to make it clear that the values derived are orientational values rather than legally binding limit values. The international comparison of quality requirements for surface waters shows that, on the whole, the national quality targets ensure a high level of protection. According to present scientific knowledge, impairments of uses, such as supply of drinking water, or risks to aquatic communities need not to be expected if the quality targets are complied with. A comparison of water quality data with the water quality targets makes it possible, on the one hand, to identify those substances whose inputs must be further reduced; on the other hand, it also shows that, for a number of substances, there is no need at present for concern over their adversely water quality. A further differentiation of the aquatic hazard potential of pollutants allows a water quality classification system to be developed on the basis of the quality targets derivation concept. The basic elements of this water quality classification system are presented, and its application is explained by way of examples.     

Closed‐form aftershock reliability of damage‐cumulating elastic‐perfectly‐plastic systems

Major earthquakes (i.e., mainshocks) typically trigger a sequence of lower magnitude events clustered both in time and space. Recent advances of seismic hazard analysis stochastically model aftershock occurrence (given the main event) as a nonhomogeneous Poisson process with rate that decays in time as a negative power law. Risk management in the post‐event emergency phase has to deal with this short‐term seismicity. In fact, because the structural systems of interest might have suffered some damage in the mainshock, possibly worsened by damaging aftershocks, the failure risk may be large until the intensity of the sequence reduces or the structure is repaired. At the state‐of‐the‐art, the quantitative assessment of aftershock risk is aimed at building tagging, that is, to regulate occupancy. The study, on the basis of age‐dependent stochastic processes, derived closed‐form approximations for the aftershock reliability of simple nonevolutionary elastic‐perfectly‐plastic damage‐cumulating systems, conditional on different information about the structure. Results show that, in the case hypotheses apply, the developed models may represent a basis for handy tools enabling risk‐informed tagging by stakeholders and decision makers. Copyright © 2013 John Wiley & Sons, Ltd.     

AOX‐Bildung bei der sonolytischen Oxidation von Salicylsäure in Gegenwart von Chlorid

AOX‐formation by the Sonochemical Treatment of Salicylic Acid in Presence of Chloride Ultrasound shows great potential for improving water, wastewater and sludge treatment processes. However, a number of questions exist: for example the influence of suspended solids or salts. In this paper the influence of chloride in view of AOX‐formation should be investigated. As organic model compound salicylic acid (0.05…1 mmol/L) was used. Formation of AOX (adsorbable organically bound halogens) was measured in dependence upon chloride concentrations (1.4…141 mmol/L) and pH 2 and 9. Ultrasound irradiation was performed in glass reactor (500 mL) at 206 kHz and 353 kHz by continuous bubbling argon:oxgen (4:1) at a flow rate of 1 L/min into the solutions. The elimination of salicylic acid and the formation of hydrogen peroxide were not influenced by the presence of chloride (up to 56 mmol/L). The rate of salicylic acid elimination and the formation rate of hydrogen peroxide are at concentrations of mmol/(L min) levels but those of AOX formation of μmol/(L min) levels. The reactions leading to chlorinated by‐products can be seen as minor reaction paths. The yield of AOX depending on frequency, pH and chloride concentration lies between 10 μg/L and 900 μg/L. In acidic medium they were twice as high as in basic medium. Below the ratio chloride : salicylic acid of 2 mol/mol, AOX could not be identified.     

Kinematic characteristics and the influence of reference velocities of phase‐shift‐plus‐interpolation and extended‐split‐step‐Fourier migration methods

The phase‐shift‐plus‐interpolation and extended‐split‐step‐Fourier methods are wavefield‐continuation algorithms for seismic migration imaging. These two methods can be applied to regions with complex geological structures. Based on their unified separable formulas, we show that these two methods have the same kinematic characteristics by using the theory of pseudodifferential operators. Numerical tests on a Marmousi model demonstrate this conclusion. Another important aspect of these two methods is the selection of reference velocities and we explore the influence of the selection of reference velocities by comparing the geometric progression method and the statistical method. We show that the geometric progression method is simple but does not take into account the velocity distribution while the statistical approach is relatively complex but reflects the velocity distribution.     

Oberflächenaktivität und bakterizide Wirksamkeit quaternärer Aminooligomere

We synthesized series of polyfunctional aminooligomers by means of condensation from polychlorparaffine with ethylenediamine. After modifying them with dimethylsulphate watersoluble oligomers of (quaternary) polyamines are obtained, which can be successfully used as biocides for treating circulating cooling-waters from different refinery plants. The products have low foaming and formed foam is unsteady. The bactericide properties of the successful samples are good. For the interval time for two to twenty hours of treatment at static conditions the microbe number value decreases by more than 99.99% at a 50 mg/dm³ dose of a biological active substance. At dosing it up to seventy-two hours the biomass is finely dispersed and does not precipitate on the walls of the chemical set-equipment.     

Post‐Synthesis of Ti‐SBA‐15 in Supercritical CO2‐Ethanol Solution

Ti‐SBA‐15 materials with Ti incorporated into the framework of SBA‐15 and controllable Ti contents were successfully prepared via a post‐treatment route in supercritical CO₂‐ethanol solution, followed by calcination. The resultant Ti‐SBA‐15 materials were characterized by means of different techniques including X‐ray diffraction, X‐ray photoelectron spectroscopy, transmission electron microscopy, IR analysis, and N₂ sorption analysis. It was demonstrated that the resultant materials retained a structure similar to that of the parent SBA‐15, and Ti was incorporated into the framework of SBA‐15. At high Ti content, i.e, Si/Ti = 5:1, a TiO₂ phase formed and was coated onto the inner surface of SBA‐15 in addition to the incorporation of the Ti in the framework. The BET surface areas of the Ti‐SBA‐15 samples decreased with increasing Ti content. The presence of small amounts of H₂O in the reaction medium may have resulted in some TiO₂ nanoparticles being uniformly distributed in the pores of the SBA‐15 accompanying the incorporation of Ti in the SBA‐15 framework.     

Visco‐acoustic prestack reverse‐time migration based on the time‐space domain adaptive high‐order finite‐difference method

It is important to include the viscous effect in seismic numerical modelling and seismic migration due to the ubiquitous viscosity in an actual subsurface medium. Prestack reverse‐time migration (RTM) is currently one of the most accurate methods for seismic imaging. One of the key steps of RTM is wavefield forward and backward extrapolation and how to solve the wave equation fast and accurately is the essence of this process. In this paper, we apply the time‐space domain dispersion‐relation‐based finite‐difference (FD) method for visco‐acoustic wave numerical modelling. Dispersion analysis and numerical modelling results demonstrate that the time‐space domain FD method has great accuracy and can effectively suppress numerical dispersion. Also, we use the time‐space domain FD method to solve the visco‐acoustic wave equation in wavefield extrapolation of RTM and apply the source‐normalized cross‐correlation imaging condition in migration. Improved imaging has been obtained in both synthetic and real data tests. The migration result of the visco‐acoustic wave RTM is clearer and more accurate than that of acoustic wave RTM. In addition, in the process of wavefield forward and backward extrapolation, we adopt adaptive variable‐length spatial operators to compute spatial derivatives to significantly decrease computing costs without reducing the accuracy of the numerical solution.