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.     

The Relation of Ca II K FEATURES TO MAGNETIC FIELD

We studied quantitatively the relation between the intensity of Caii K-line bright features and the intensity of the associated magnetic elements using two data sets obtained at the Big Bear Solar Observatory. Both network and intranetwork (IN) structures were considered. Magnetic field changes always affected the K-line emission; for example, the appearance of new bipoles was always followed by enhanced K-line emission. There is an almost linear correlation between the K-line intensity and the magnetic field strength of the stronger network elements (elements with absolute field strength higher than 11–19.5 G). We identified two classes of intranetwork K-line elements: magnetic and non-magnetic ones. The number of the magnetic K-line IN elements above a 1-sigma threshold was only 5%–10% of the number of the non-magnetic ones. The magnetic K-line IN elements were almost 3 to 4 times brighter compared to the non-magnetic elements. On the other hand, the non-magnetic elements were moving with typical velocities of 35–40 km s^–1 while the velocities of the magnetic K-line elements were of the order of 1 km s^–1.     

Possible formation scenarios for the giant H i envelope around the NGC 4490/4485 system

We present observations of H i in the nearby interacting galaxies NGC 4490 and 4485 made with the VLA in both C and D arrays. The galaxies are embedded in an extensive envelope of neutral hydrogen which is elongated in a direction approximately perpendicular to the plane of NGC 4490, with an extent of about 56 kpc. We argue that this distribution of neutral hydrogen can best be explained by a galactic-scale bipolar outflow of H  i driven by supernovae in NGC 4490. The flow from the disc appears to be reasonably well collimated and has probably persisted for approximately 6 × 10⁸ yr. The implications for galaxy evolution when such mass loss occurs are briefly discussed.     

The Néel transition and magnetic properties of terrestrial,synthetic, and lunar ilmenites

The magnetic susceptibility of a terrestrial, synthetic and lunar ilmenite specimen has been measured from 4 to 300 K. All specimens had a single Néel temperature transition which ranged from 56 to 57.7 K. In one case the powdered specimen was partially aligned in the magnetic field prior to the susceptibility measurements and the Néel transition was observed to shift to 60 K indicating magnetic anisotropy. A study of several magnetic parameters calculated from the experimental data showed gross impurities in the terrestrial specimen, single-domain to multi-domain metallic iron in the synthetic specimen, and a small amount of superparamagnetic metallic iron in the lunar sample. No multidomain iron was observed in the lunar ilmenite. The results of electron spin resonance measurements were also in general agreement with these findings. Because of the absence of Fe³⁺ compared to most terrestrial samples it is suggested that the anisotropic magnetic parameters be determined on lunar ilmenite when a large enough single crystal becomes available.     

Die Roßfeldschichten: Ein Beispiel für Sedimentation im Bereich einer tektonisch aktiven Tiefseerinne aus der kalkalpinen Unterkreide

Zusammenfassung Im Mittelabschnitt der Nördlichen Kalkalpen (Ostalpen), zwischen den Flüssen Saalach und Traun, in einer streichenden Verbreitung von 50 km, entwickeln sich in der Unterkreide aus den neokomen Aptychenschichten (Schrambachschichten) die terrigenen Gesteine der Roßfeldschichten. In dieser Studie wurde das Profil der Typlokalität am Roßfeld südlich von Salzburg untersucht.Die Unteren Roßfeldschichten bestehen in ihrem tieferen Abschnitt aus einer ca. 175 m mächtigen Mergelgruppe. Darüber folgen 10–15 m dünnbankige Sandsteine, die in eine 70–80 m mächtige, dickbankige Sandsteingruppe übergehen. Die Oberen Roßfeldschichten setzen abrupt mit grobklastischen Gesteinen ein. Die gesamte Schichtfolge zeigt eine Kornvergröberung gegen das Hangende.Eine erste stichprobenartige mikropaläontologische Bearbeitung hat im tieferen Anteil des Profiles gut auswertbare Foraminiferenvergesellschaftungen erbracht, die mit einer Reihe stratigraphisch wertvoller Unterkreidearten das von den Roßfeldschichten dieser Region nach ihrer Ammonitenfauna bekannte Alter Obervalendis—Hauterive bestätigt.Das Profil konnte im Vergleich mit rezenten Faziesverteilungen als eine vorstoßende Serie eines Tiefseerinnen-Environments interpretiert werden. An Subenvironments sind der Bereich der Hauptrinne (= dickbankige Sandsteingruppe), ein beckenwärts gelegener Damm (dünnbankige Sandsteinfazies) und daran anschließend ein submarines Überflutungsgebiet (= Mergelgruppe) zu unterscheiden. Von der Beckenabhangseite her hat sich ein kleinräumiges Fächersystem mit Grobklastika und Slumping-Ablagerungen vorgeschoben Obere Roßfeldschichten).Das terrigene Material der Roßfeldschichten ist durch das Auftreten von Chromspinell und grüner Hornblende in den Schwermineralspektren charakterisiert. Besonders interessant sind vereinzelt vorkommende rotbraune Hornblenden (Kaersutit), welche auf ein Vorkommen von Alkaligesteinen im Liefergebiet Hinweis geben. Die Anlieferung des terrigenen Materials erfolgte von einer südlich gelegenen Provinz, die eine orogeninterne Position innehatte. Die Position entspricht nicht jener des Ultrapienidischen Rückens im Cenoman und zur Zeit der tieferen Gosauschichten.

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Summary The Lower Cretaceous Roßfeld Formation, which is exposed in the central Northern Calcareous Alps (East Alps) between Saalach river and Traun river over a distance of about 50 km, was studied in a profile in the type locality at the Roßfeld south of Salzburg. The terrigeneous rocks of the Roßfeld Formation arise gradually from the Neocomian Aptychus beds (Schrambachschichten).In its deeper part the Lower Roßfeld Fm. consists of gray marls of about 175 m thickness. Above that 10–15 m thin-bedded sandstones and then 70–80 m thick-bedded ones follow. The Upper Roßfeld Fm. starts abruptly with coarse-grained sediments. The complete sequence is a coarsening-upward unit.As a result of an initial micropaleontological study well evaluable foraminifera associations were found in the lower part of the section. Some stratigraphically significant species of Lower Cretaceous age attest the range from Upper Valanginian to Hauterivian already established by ammonites in this region.According to modern facies distributions the Roßfeld Fm. can be interpreted as a prograding deep sea channel facies. The following subenvironments are observed: The axial channel (= Thick-bedded sandstone group), and a seaward levee (= thin-bedded unit) passing into a submarine overbank facies (= marly unit). At the slopeward side of the channel there was a narrow fan system consisting of coarse-grained components and slump-deposits (= Upper Roßfeld Fm.).The heavy mineral spectra of the terrigeneous material of the Roßfeld Fm. are characterized by the occurrence of chromium spinell and green amphiboles. Very interesting are few reddishbrown amphiboles (kaersutite), which are considered to indicate alkaline rocks in the source area. This source area was lying in the south in an internal position of the East Alpine system. This position was not the same as that of the Ultrapienidic Ridge of Cenomanian or early Gosauian age.

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Résumé Dans le partie moyenne des Alpes Calcaires Septentrionales entre les rivières Saalach et Traun, les couches terrigènes de la Formation de Rossfeld se développent à partir de la série marneuse de Schrambach (couches à Aptychus) du Néocomien. Cette étude présente les résultats de l'examen de la localité typique des couches de Rossfeld au sud de Salzburg.Les couches inférieures de Rossfeld sont formées à leur base par des marnes grises d'une épaisseur de 175 m environ. Au-dessus suivent 10–15 m d'un grès en minces bancs qui passe à des grès en gros bancs d'une épaisseur totale de 70–80 m. Les couches supérieures de Rossfeld commencent brusquement avec des sédiments grossiers. La série complète montre une augmentation de la granularité vers le haut.Une étude micropaléontologique préliminaire révèle des faunes à foraminifères à espèces typiques du Crétacé inférieur (Valenginien à Hauterivien) dans la partie inférieure de cette section des couches de Rossfeld.Par comparaison avec des répartitions de facies récentes, on peut interpréter la formation de Rossfeld comme facies d'une série qui s'avance dans la région d'une fossé abyssal. On peut définir les régions spéciales suivantes: Un canal axial avec des grès en gros bancs, une levée du côté du bassin avec des grès en bancs minces et, lié à cela, un terrain de débordement sousmarin avec la série marneuse. Un éventail plus local à matériel détritique plus grossier et avec des structures de slumping s'avançait à partir du flanc du bassin: ce sont les couches supérieures de Rossfeld.Le spectre des minéraux denses de la formation de Rossfeld est caractérisé par l'existence du spinelle chromé et d'amphiboles vertes. Particulièrement intéressantes sont des amphiboles rouge-brun très rares (Kaersutites), lesquelles montreraient l'existence de roches alcalines dans le domaine nourricier. Le matériel détritique a une origine méridionale et provient donc d'une région ayant une position interne dans l'orogène, ce qui ne correspond pas avec la position du seuil ultrapiénidique du crétacé supérieur.

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Arbeit durchgeführt im Rahmen des IGCP-Projektes Mid-Cretaceous Events 73/ I/58.     

Employment in retailing: A case study of employment in suburban shopping centres

There have been many studies of the retail industry in recent years, and of the impact that retailing has had on the spatial arrangement of urban areas and on consumer behaviour. Little attention has been paid, however, to employment in retailing, which is disturbing in view of its growing importance and its rapidly changing nature and composition. This paper examines the nature of the broad structural changes within the industry, and investigates their spatial consequences through a case study of employment generation within a system of suburban retail centres in Canberra, Australia. It is shown that the evolution of suburban centres, particularly those of a regional variety, has had an important and enriching impact on the suburban labour market. The regional centres are also seen to be the focus of the major structural employment changes currently affecting the retail industry. This has some important implications for urban planning.     

The origin of the Nicaraguan depression

A conspicuous graben extends for 800 kilometers through El Salvador and western Nicaragua to the Caribbean Sea in northeastern Costa Rica. Like the smaller but structurally similar Semangko and Toba Depressions of northern Sumatra, the trough is clearly related to voluminous volcanic eruptions during Late Tertiary time. In the region around Lakes Managua and Nicaragua, where the depression is best defined and reaches its greatest dimension, a thick series of Tertiary sediments and volcanic rocks provides a means of interpreting the Cenozoic history of the region. Following a long period of intermittent volcanic activity and sedimentation, extensive sheets of andesitic and dacitic ignimbrites were erupted during Late Miocene time from fissure sources which appear to have been located near the now-subsided central portion of the graben. Near the coast, ignimbrites flowed across a flat lagunal shore overwhelming and burying the tropical vegetation and finally coming to rest in shallow water. Unusual textures and chaotic mixtures of pumice with sediments and silicified wood characterize the bases of many of the water-laid ignimbrites. Subsidence of the graben does not appear to have occurred concurrently with the ignimbrite eruptions but followed them closely near the end of the Miocene or the beginning of Pliocene time. Subsequent activity has been confined to relatively smaller eruptions from central vents near the boundary faults of the graben.