Alternative Validation of a LC-MS/MS-Multi-Method for Pesticides in Drinking Water

The development of instrumental analytics such as the LC-MS/MS has made it possible to quickly determine many component concentrations in a single chromatogram. However, the validation of such multi-methods needs new strategies for robustness and optimization. Statistical execution of analytical tests is one tool that can be utilized to meet this requirement. A Central Composite Design (CCD) was utilized for the validation of an LC-MS/MS multi-method for 84 analytes. The experimental design includes six design variables and two non-design variables (response variables). Concentration, ionization temperature, dwell time, gradient, flow (of eluent), and spraying/curtain gas (continuous design variables) were varied on five different levels; the whole design encompassed 91 runs. To investigate the robustness of a LC-MS/MS method both peak sensitivity and chromatographic separation had to be verified. Therefore, two non-design variables were necessary. The distribution of the peaks over analysis time was applied to describe the quality of the chromatographic separation. The sensitivity was described with the signal to noise ratio (S/N). The evaluation of the measured data was accomplished with the Analysis of Variance (ANOVA) and the Response Surface Methodology (RSM). Three main effects (concentration, ionization temperature, dwell time) and no significant interaction effect were found for the response variable “S/N”. The variables of concentration, ionization temperature, and dwell time had no significant effects for the response variable “S/N”. The ANOVA of the response variable chromatographic separation abandoned no significant effects as well. Therefore, robustness of the method can be guaranteed for all non significant design variables.     

Modern diatom, cladocera, chironomid, and chrysophyte cyst assemblages as quantitative indicators for the reconstruction of past environmental conditions in the Alps. II. Nutrients

Surface sediments from 68 small lakes in the Alps and 9 well-dated sediment core samples that cover a gradient of total phosphorus (TP) concentrations of 6 to 520 g TP l^-1 were studied for diatom, chrysophyte cyst, cladocera, and chironomid assemblages. Inference models for mean circulation log₁₀ TP were developed for diatoms, chironomids, and benthic cladocera using weighted-averaging partial least squares. After screening for outliers, the final transfer functions have coefficients of determination (r², as assessed by cross-validation, of 0.79 (diatoms), 0.68 (chironomids), and 0.49 (benthic cladocera). Planktonic cladocera and chrysophytes show very weak relationships to TP and no TP inference models were developed for these biota. Diatoms showed the best relationship with TP, whereas the other biota all have large secondary gradients, suggesting that variables other than TP have a strong influence on their composition and abundance. Comparison with other diatom – TP inference models shows that our model has high predictive power and a low root mean squared error of prediction, as assessed by cross-validation.     

Cladocerans and chironomids as indicators of lake level changes in north temperate lakes

Water level fluctuations affect the size of the pelagic zone relative to the size of littoral habitats, and thus may influence the relative abundance of remains from planktonic and littoral cladocerans in sediment. The application of this planktonic/littoral ratio for the reconstruction of past water level changes is discussed using examples of: (1) surficial profundal sediments from lakes of different water depths; (2) Holocene variation in a profundal sediment core; (3) horizontal variation in surficial sediments within a lake; and (4) long term variation in an inshore sediment core. The latter seemed to be the most promising application of this ratio. Maximum effects of water depth changes on the lake fauna are expected in the littoral zone. It is, however, difficult to read this effect directly from subfossil cladoceran and chironomid assemblages from inshore sediments as shown by a sediment profile from a site exposed to a long term decrease of water depth.     

Fidelity and time resolution of the magnetostratigraphic record in Siwalik sediments: high-resolution study of a complete polarity transition and evidence for cryptochrons in a Miocene fluviatile section

The Surai Khola section in southwest Nepal, a 5000 m continuously exposed record of fluvial sedimentation since Middle Miocene, was revisited for high-resolution magnetostratigraphy in sequences with expected cryptochrons and reversals of the geomagnetic field. Polarity intervals with durations of a few tens of thousands of years are recorded as zones of stable palaeomagnetic directions. Polarity transitions are recorded as zones with complex demagnetization behaviour of specimens in the sedimentary column. Almost antiparallel palaeoremanence directions, residing in different haematite phases in the same specimens, could generally not be separated properly by thermal demagnetization. Differing demagnetization paths for neighbouring specimens during a reversal suggest that measured transitional directions are not true geomagnetic field directions, but rather are generated by the superposition of variable amounts of at least two almost antiparallel components of magnetization. Accompanying studies of recent river sand deposits demonstrate that these sediments acquire a true depositional remanent magnetization (DRM) with considerable inclination errors and scattered directions for individual specimens.     

The exceptional Oder flood in summer 1997 — distribution patterns of the oder discharge in the Pomeranian Bight

The exceptional Oder flood in summer 1997 was a unique event in order to investigate the impacts on and the consequences for the ecosystem of the Baltic Sea of about 6.5 km³ additional water loaded with nutrients and contaminants and discharged within only 5 weeks. About 15 institutions participated in this investigation in both the Szczecin Lagoon and the Pomeranian Bight. The Baltic Sea Research Institute Warnemünde studied the water and nutrient inflow, the spreading of the Oder discharge, and the impact of the discharge on the ecosystem. The main topic of the presented investigations is a detailed study of the spatial and temporal spreading of the extreme river discharge in the Pomeranian Bight and the southern Baltic Sea by satellite data, ship observations and continuous buoy measurements as well as numerical modelling. The meteorological conditions were characterized by mainly easterly winds which guided the outflowing riverine water along the German coast into the Arkona Sea. The spatial and temporal development of the distribution patterns of the Oder discharge was monitored by about 80 Sea Surface Temperature (SST) images of NOAA satellites. Shipborne measurements showed that the vertical extent of the Oder plume ranged between 5 and 7 metres. The concentrations of inorganic nutrients, except higher silicate, were comparable to typical winter/early spring values (seasonal maximum) in this region. The high dilution effect of the flood water reduced the concentration of contaminants and thus, prevented a direct negative impact of trace metals and chlorinated organic compounds on the marine environment. Coupled physical-biochemical modelling in combination with SST-images demonstrated the temporal development and satellite data in the visible spectral range delivered the maximum extent of discharged river water into the southern Arkona Sea where a further western transport was limited by the upwelling region off Hiddensee. Thus, all detected effects of the Oder flood were confined to the Pomeranian Bight and the southern Arkona Sea, without long-term consequences for the ecosystem.     

Plate kinematics and the gravity field

Both the system of plate motions and the global gravity field or the geoid are now so precisely known that it seems worthwhile to look for quantitative relationships. Some aspects, such as the general occurrence of positive gravity and geoid anomalies in regions of plate convergence, have long been known. Our aim is to describe the gravitational field in terms of plate-kinematic parameters and we present a preliminary step in this direction: for four plates (Pacific, Nazca, Indian, American) we have computed the correlation of the Gem 8 geoid heights (with reference to an ellipsoid of 1/298.255 ellipticity) with distance from the poles of motion and distance from the axes in an “absolute” frame. The geoid tends first to drop from the ridge axes to at least 10° distance and then to rise toward the convergence zones. This trend is strongest for the Indian plate in collision with Eurasia, is smaller, but very clear for the oceanic Pacific and Nazca plates, and is not developed for the American plate which does not subduct. We did not find a consistent relationship for the geoid with distance from the pivots. A possible interpretation of the results is the return flow of the large-scale mantle circulation.     

On the relation between residual currents and the wind field in the German Bight

Summary The long-period part (T>25 h) of currents measured at close spacing in the German Bight in June 1968 is investigated. The north component of the bottom current is shown to be highly correlated with the east component of the wind in this area, the wind-generated changes of the mass-field giving rise to a quasi-geostrophic current near the bottom.This current responds without perceptible delay to the variations of wind fields with periods considerably longer than those of the seiches of the North Sea. The accelerations linked to such long periods are so small as to be negligable and the residual currents can be regarded as quasi-stationary.

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Über die Beziehung zwischen Reststrom und Windfeld in der Deutschen Bucht

Zusammenfassung Es werden engabständige Strommessungen in der Deutschen Bucht aus dem Juni 1968 in ihrem langperiodischen Teil (T>25 h) untersucht. Dabei ergibt sich, daß die Nordkomponente des Bodenstromes (v) stark korreliert mit der Ostkomponente des Windes (U) in diesem Gebiet. Die winderzeugten Veränderungen des Massenfeldes verursachen eine quasi-geostrophische Strömung am Boden.Diese Strömung reagiert ohne erkennbare Verzögerung auf solche Veränderungen des Windfeldes, die erheblich größere Perioden haben als die Eigenschwingungen der Nordsee. Die damit verbundenen Beschleunigungen sind sehr klein und so zu vernachlässigen; daher kann man die Restströmung auch als quasi-stationär ansehen.

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Sur la relation entre les courants résiduels et le champ du vent en baie Allemande

Résumé La partie à longue période (T>25 h) de courants measurés en des points rapprochés en baie Allemande en juin 1968 est étudiée. La composante Nord du courant de fond se révèle largement corrélée avec la composante Est du vent dans cette zone. Les modifications du champ de masse dues au vent donnent naissance à un courant quasi-géostrophique près du fond.Ce courant répond sans délai perceptible aux variations du champ du vent avec des périodes considérablement plus longues que celles des seiches de la mer du Nord. Les accélérations liées à de telles longues périodes sont si petites qu'elles peuvent être négligées et les courants peuvent être considérés comme quasi-stationnaires.