Ermittlung der Nachweis-, Erfassungs- und Bestimmungsgrenze nach DIN 32645 mit Hilfe eines Programms Calculation of Detection Limit,Identification Limit and Determination Limit according to DIN 32645 with the Aid of a Computer Programs

The new German standard specification DIN 32645 defines detection, identification and determination limit of analytical experiments and contains formulas for their calculation. The detection limit is a qualitative value, only at the determination limit a quantitative statement is possible. The identification limit is no limit of decision for analyses. The expenditure for calculating these parameters is considerable. Therefore, a computer program was developed and tested at the analysis of herbicides with GC-MS after enrichment with solid phase extraction (SPE). It proved that the program is also very useful at the development of analytical methods, because it allows a quick examination of changes of the analytical method. After optimization detection limits for the herbicides were achieved which amount 10–20% of the limit of the German drinking water regulation.     

Mixture model based multivariate statistical analysis of multiply censored environmental data

Environmental data are commonly constrained by a detection limit (DL) because of the restriction of experimental apparatus. In particular due to the changes of experimental units or assay methods, the observed data are often cut off by more than one DL. Measurements below the DLs are typically replaced by an arbitrary value such as zeros, half of DLs, or DLs for convenience of analysis. However, this method is widely considered unreliable and prone to bias. In contrast, maximum likelihood estimation (MLE) method for censored data has been developed for better performance and statistical justification. However, the existing MLE methods seldom address the multivariate context of censored environmental data especially for water quality. This paper proposes using a mixture model to flexibly approximate the underlying distribution of the observed data due to its good approximation capability and generation mechanism. In particular, Gaussian mixture model (GMM) is mainly focused in this study. To cope with the censored data with multiple DLs, an expectation–maximization (EM) algorithm in a multivariate setting is developed. The proposed statistical analysis approach is verified from both the simulated data and real water quality data.     

线性波浪加载下海底斜坡失稳机制的数值分析

基于大型有限元软件ABAQUS中的荷载模块,添加一阶波浪力载荷模式,并结合强度折减技术,实现波浪力作用下海底斜坡稳定性与失稳机制的弹塑性有限元数值分析。引入典型算例,利用先前提出的波浪荷载下海底斜坡稳定性的极限分析上限方法开展数值解的对比验证;在此基础上,通过深入地变动参数比较分析,探讨不同波长、波高和水深等波浪参数对计算结果的影响以及波浪力影响下海底斜坡潜在滑动面的变化规律,获得波浪荷载下海底斜坡失稳滑动机制的初步认识。     

On-Line Monitoring mit Biosensoren am Gewässer zur ereignisgesteuerten Probenahme

Biosensors for On-Line Monitoring of Waterways for Sample Taking Aimed at Relieving Disturbances. There is a generally accepted need for rapid, simple and low cost online water quality monitors. Besides the chemophysical analytical methods the biological and biochemical methods are of increasing importance for the integral monitoring of pollutants. Electrodes made up of cyanobacteria, i.e. Synechococcus, for immediate detection of acute toxic effects of pollutants, are used as a biosensor. The measurements of the photosynthetic electron transport system PETS under alternating light–dark conditions, are conducted in a flow-through cell against reference electrodes (Ag/AgCl). A mediator (Fe(II)/Fe(III)) makes the flow of current possible. The time which the electrode takes to react is about two minutes, and a multiple confirmed result is available after ten minutes (Detection limit for Atrazine = <20 μg/L Atrazine). Similar investigations were done with an E. coli-electrode.     

River Seepage Conductance in Large‐Scale Regional Studies

Flow exchange between surface and groundwater is of great importance be it for beneficial allocation and use of water resources or for the proper exercise of water rights. In large‐scale regional studies, most numerical models use coarse grid sizes, which make it difficult to provide an accurate depiction of the phenomenon. In particular, a somewhat arbitrary leakance coefficient in a third type (i.e., Cauchy, General Head) boundary condition is used to calculate the seepage discharge as a function of the difference of head in the river and in the aquifer, whose value is often found by calibration. A different approach is presented to analytically estimate that leakance coefficient. It is shown that a simple equivalence can be deduced from the analytical solution for the empirical coefficient, so that it provides the accuracy of the analytical solution while the model maintains a very coarse grid, treating the water‐table aquifer as a single calculation layer. Relating the empirical leakance coefficient to the exact conductance, derived from physical principles, provides a physical basis for the leakance coefficient. Factors such as normalized wetted perimeter, degree of penetration of the river, presence of a clogging layer, and anisotropy can be included with little computational demand. In addition the river coefficient in models such as MODFLOW, for example, can be easily modified when grid size is changed without need for recalibration.     

基于地面实测光谱的太湖水体富营养化水平估算

富营养化指数是评价水体污染情况的一个重要的综合性指标．通过对高光谱遥感数据和水体富营养化指数的分析,确立了反演水体富营养化水平的高光谱敏感波段,进而用选择的敏感波段和波段组合来建立模型．通过对几个模型的比较,选出了较为理想的估算模型．最后对模型进行精度分析,认为该模型具有一定的可靠性和实用性．从而确定了直接由高光谱遥感数据监测水体富营养化水平的可能性,为实现由高光谱遥感数据开展大范围的水质调查奠定了一定的理论基础．     

边坡稳定性分析及滑移面快速确定

针对边坡稳定性分析及滑移面确定这一工程问题,提出一种解析法。首先根据基本假设及边坡的几何关系,建立边坡滑移面确定模型,推导出滑移面控制方程;然后基于极限平衡理论,采用解析的方法推导出与滑移面控制方程相关联的安全系数解析表达式;最后通过求解目标函数（一元函数）在定义域上的最小值,求出边坡最小安全系数及对应的临界滑移面。通过算例验证表明：本文方法的边坡稳定性分析结果与传统极限平衡条分法分析结果基本一致,最小安全系数偏差不超过±5%;本文方法所确定的临界滑移面与基于传统极限平衡条分法所广泛搜索的临界滑移面比较接近。本文方法对于高效、精准地进行边坡稳定性分析及滑移面确定具有借鉴意义。     

Determination of radionuclides in water at uranium mining remediation – a comparison of analytical methods

The corporate purpose of Wismut GmbH is to decommission its former mining holdings and to rehabilitate the landscape and the environment. Sample taking and analysing the value of contaminants are necessary steps for the remediation of waste rock piles, the recycling of contaminated areas, controlled flooding of uranium mines. Main emphasis lies on the determination of heavy metals and radionuclides of natural decay chains of U‐238 and U‐235. Yearly about 60 000…70 000 determinations of radionuclides in waters were done. Facing this high output of determinations it is a permanent task for laboratory and quality management to ask: Are the results of different methods comparable to each other? Is there a preferred analytical technology? Which matrix influences exist? and What about the analytical costs? Answers to these important questions are given in this report. Summarizing our investigations done in the last few years it is possible to say that – by using different analytical methods the results of radionuclides in water samples (surface or groundwater) are comparable, – a not negligible influence of Ra‐223, Ra‐224 and Ra‐228 may exist by using the DIN 38404 C18 method to determine Ra‐226, – a preferred method cannot be defined, – the choice of the analytical method should include analytical questions (the sample matrix, the occurrence of other disturbing radionuclides, the necessary detection limit) and economical questions (costs, other parameters to be determined).     

A Systematic Approach for Evaluating the Quality of Ground Water Monitoring Data

The recognition and assurance of the quality of ground water monitoring data are crucial to the correct assessment of the magnitude and extent of a ground water contamination problem. This article addresses an approach being developed to systematically evaluate the quality of a given set of ground water monitoring data collected during site investigation/ remedial action efforts. The system consists of a checklist of criteria, grouped into four major categories, which can be applied to laboratory or field measurements.
The first category, basis of measurement, considers whether the appropriate sampling, boring and/or analytical methods were chosen to obtain the measurement and the limitations of each method. Secondly, application of the method is assessed. This includes examination of the extent to which procedures were correctly performed, the use of quality control measures and calibration, and possible sources of error in the measurements. Third, evaluation of applied statistical methods is made, with consideration given to which statistics are meaningful in a given context and whether measurements are reproducible. The final category, corroborative information, considers whether independent data or other information are available that add credibility to the values measured.
In this approach, a "high quality" data value is defined as one in which accuracy is supported by meeting the preceding criteria. When accompanied by precision information, high quality data allow for defensible assessments and actions. This evaluation system is useful in developing monitoring programs and in guiding documentation of field and laboratory methods during data collection. It relies heavily on experienced judgment and can be catalyst for the beneficial exchange of knowledge and ideas among ground water professionals.     

Use of Observations below Detection Limit for Model Calibration

Censored (nondetect) values occur when chemical concentrations in water samples are near or below the level that can be measured by an analysis method. It is common to either delete or substitute values for nondetect observations for use in model calibration, but this practice can bias the estimated parameter values and the model predictions. A more realistic representation of the system is obtained from the calibration if we include such observations in a manner reflecting that we know only the value is below the detection limit. Consequently, we propose use of the censored-residual approach to including nondetect values as observations for calibration. In this approach, residuals are calculated as the detection limit minus the simulated value when the simulated value exceeds the detection limit, and the residual is assigned a value of zero when the simulated value is below the detection limit. The new censored-residual approach is particularly advantageous when calibrating transport models to low concentration data.     

Spatial distribution and comparative evaluation of phosphorus release rate in benthic sediments of an estuary dam

A series of experiments and simulations were performed to ascertain the rate at which phosphorus is released using a water quality model in Saemangeum Lake, an artificially constructed lake located in an estuary. The general inflow of seawater once a day contributed to the formation of a halocline in the lake water, which caused variation in the vertical concentration of dissolved oxygen. The halocline was mainly observed in the deep downstream regions of Saemangeum Lake that are close to the op...     

Water Quality Modeling and Dissolved Oxygen Balance in Streams: A Point Source Streeter‐Phelps Application in the Case of the Harsit Stream

The Harsit Stream flowing into the Black Sea is an important watershed in the northeastern part of Turkey. The monthly averages of dissolved oxygen, carbonaceous biochemical oxygen demand, temperature, pH, total suspended solids, total phosphorus and total nitrogen were obtained for the water samples taken from the Tekke, Akcakale and Haciemin sites of the Harsit Stream. Water quality parameters were analyzed and evaluated according to the WHO standards and the Turkish Water Pollution Control Regulation. Initially, the variations in the dissolved oxygen profile were determined from dissolved oxygen, temperature and carbonaceous biochemical oxygen demand measurements by using the point source Streeter‐Phelps equation. Critical dissolved oxygen deficit values were calculated for the monthly average from January–December 2005, which are below the limit value (4 mg L^–1) excluding April (7.26 mg L^–1) and May (5.98 mg L^–1) in the Harsit Stream, resulting in it having second class water quality in terms of dissolved oxygen concentration, temperature, pH and biochemical oxygen demand. It is also seen that the minimum dissolved oxygen limit value (8 mg L^–1), which is a desired quantity for drinking water, is under the limit value for all months in the case of the water mixture. In particular, during the summer months, the consumption speed of oxygen is greater than the production speed of oxygen with increasing temperature and decreasing discharge, and negative values (anoxia) of dissolved oxygen sag are seen. These situations call for significant precautions and treatment criteria.     

Trends in water quality variations in the Odra River the day before implementation of the Water Framework Directive

This paper contains an account of UN/EEC-sponsored research on water quality monitoring and assessments in the catchments areas of Europe's 10 transboundary rivers. In this context, water quality assessments established on the basis of monitoring data for Poland's rivers are discussed. Consideration is also given to the water quality assessment methods recommended by the EU Directives. The problem has been exemplified by the analysis of water quality variations in the transboundary river Odra in the time span of 1973–2003. For the years 1993–2003, the trends in water quality variations are calculated and the rates of variation are analysed. The points in time when the water quality will have attained the second class purity values are predicted, taking into account the requirements specified in Polish, Czech and German standards. Analysis of the trends in the variations of pollution parameters has revealed that the achievability of good water quality depends on the limit values adopted for the assessment.     

Probleme der Wasserkontamination und ihrer analytischen Erfassung

The increasing loading of raw water for the drinking water supply with trace substances results in an increasing exposure of the population to toxicologically suspect substances. At present, the quality of such raw waters is evaluated mainly by cumulative parameters or individual substances with low eco- or humantoxicological relevance. Now, about 5 · 10⁵ environment-relevant organic substances must be taken into account, the number of individual compounds for a loaded receiving water being estimated to be 10³. Secondary contaminations are caused by oxidative processes of water treatment. In the trace substance analysis so far only about 40% of the organic substances are isolable by comparatively simple methods. From this derives the demand for developing standardized methods for determining cumulative and group parameters with a high value of information and indication, as e. g. organically bonded chlorine or halogens.     

基于系统动力学的巢湖流域水资源承载力动态预测与调控

湖泊流域水资源承载能力动态预测与调控是维护湖泊生态安全、保障社会经济健康持续发展的重要基础和手段.本文以巢湖流域为研究对象,提出基于系统动力学的湖泊流域水资源承载力动态预测技术和试验优化调控方法.首先以县(市)为基本单元构建水资源承载力系统动力学模拟与动态预测模型;再从空间上将各县(市)耦合为流域系统整体模型,并通过敏感性分析筛选量质要素调控指标;最后采用正交试验设计确定流域水资源承载力优化调控方案.结果表明:由于流域内产业规模的扩大以及城镇化率的提升,20172050年巢湖流域水资源承载状态值整体呈恶化趋势,并于2030年以后将长期处于超载状态,通过对影响要素针对性优化调控后,20172050年流域水资源承载状态均达到临界或可载.研究表明本文提出的方法对于促进区域社会经济环境协调发展和改善流域水资源承载力具有较好的实际应用价值.     

基于“水文频率-水质”拟合曲线的河流水质变异与等级特征值分析方法

时空特征分析对全面掌握水质变异规律具有重要意义,但现有的水质时空特征分析方法仍存在水质变异次序不分、水质变幅极值不清、水质评价特征值不明等不足。为更加清晰地探析水质时空特征信息,以秦淮河为研究对象,参考工程水文学经验频率法,建立“水文频率-水质”拟合曲线用于探索流域内高/低活动区不同时间段和丰/枯水期不同河段水质变异特征,并与传统的箱线图法进行对比。结果表明:与箱线图相比,“水文频率-水质”拟合曲线可量化关键水质评判点与特征值信息,使水质时空变异过程更为清晰。在时间上“水文频率-水质”拟合曲线的最佳形式为线性曲线,水质浓度一般不会发生突变;在空间上“水文频率-水质”拟合曲线的最佳形式为指数曲线,水质浓度有较大可能发生突增。各时间段高活动区氮磷浓度大于低活动区,各水体断面丰水期氮磷浓度低于枯水期。该方法分析过程简单方便,结果直观有序,能将水质信息以统计规律自动反映出来,在水质采样点、采样时间和采样频率典型时可作为优选方法用于河流水质时空特征研究。     

Die Nitratsituation in der Bundesrepublik Deutschland

Altogether 10… 20 kg/ha·a N from precipitation are introduced into the soil. The fertilization of the agriculturally used area increased from 50 to 120 kg/ha·a N between 1950 and 1982. The nitrogen concentration is theoretically increased by 0.4 mg/l due to infiltration of surface water and wastewaters. The data prove agriculture to the main source of the nitrate load of groundwater, especially in regions with predominantly intensive agricultural use there is delivered drinking water with nitrate concentrations of more than 50 mg/l. The fixing of the limit value for drinking water at 50 mg/l nitrate (value recommended by the EC: 25 mg/l) is justified by new findings. Since the technology of nitrate elimination from water is very expensive, mainly the preventing of too high nitrate concentrations should be aimed at by agricultural measures of ground-water protection.     

Earthquake analysis of concrete gravity dams including reservoir bottom absorption and dam-water-foundation rock interaction

The available substructure method for the earthquake analysis of concrete gravity dams, including the dynamic effects of the impounded water and the flexible foundation rock, is extended to include the effects of alluvium and sediments invariably present at the bottom of actual reservoirs. Modelled approximately by a reservoir bottom that partially absorbs incident hydrodynamic pressure waves, these effects are incorporated into the continuum solution for the hydrodynamic pressure. The dam-water-foundation rock system is idealized as a two-dimensional system and analysed under the assumption of linear behaviour. An example earthquake analysis is presented to demonstrate the results obtained from the analytical procedure. Computation times for several cases illustrate the efficiency of the analytical procedure. In particular, the additional computation time required to include reservoir bottom absorption is shown to be very small.     

Sectional response of T-shaped RC walls

Deformation quantities such as strain, curvature and displacement are of paramount importance in seismic design within a performance-based procedure that aims to control the structural response at predefined levels of inelastic action. Given the importance of curvature expressions independent of strength for the design process, and for the particular case of T-shaped walls, the curvature trends at yield, serviceability and ultimate limit state are determined in graphical and analytical form. The comprehensive set of equations proposed in this work are strength independent and allow the reliable computation of limit-state curvatures, essential in a displacement-based design approach, and thus the realistic estimation of appropriate ductility factors in the design of T-shaped walls. Furthermore, results regarding the section properties of T-shaped walls, such as the elastic stiffness and the moment capacity for opposite directions of loading, offer additional information on T-shaped walls.