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.     

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.     

Atmospheric noble gases in volcanic glasses from the southern Lau Basin: origin from the subducting slab?

Noble gas concentrations and isotopic compositions have been determined for four submarine volcanic glasses from the Valu Fa Ridge (VFR) in the southern Lau Basin. The samples are the least differentiated ones from this area, and they display enrichments in fluid-mobile elements similar to the nearby island arc. ³He/⁴He ratios are slightly below average MORB (6.8–7.8 times atmospheric), whereas Ne, Ar, Kr, and Xe have isotopic compositions very similar to air. Together with previously published data from the Valu Fa Ridge and other spreading segments in the Lau Basin, our data show a systematic latitudinal variation of increasing Ne, Ar, Kr, and Xe abundances from north to south as well as Ne and Ar isotopic compositions changing from MORB-like to atmosphere-like in the same direction. Moreover, isotopic compositions and noble gas abundances of the lavas correlate strongly with Ba/Nb ratios and H₂O concentrations. Based on these observations and mass balance arguments, we propose that the atmospheric noble gases come from the subducting oceanic crust and are not due to shallow contamination with air dissolved in seawater or assimilation of old crust. Our data suggest that the noble gases released from the subducting slab are atmospheric and thus contain little or no solar He and Ne. In addition to the fact that ratios of He to heavy noble gases are small in aged ocean crust, He has possibly fractionated from the other noble gases due to its higher diffusivity, and thus He transport from the subducting slab into the mantle wedge is probably insignificant. We propose that the ³He/⁴He ratios lower than MORB observed in the VFR lavas result from radiogenic ingrowth of He in a highly depleted, and hence degassed, mantle wedge after the enrichment of U and Th released from the downgoing slab.     

Late Pleistocene outburst floods from Issyk Kul,Kyrgyzstan?

Elevated shorelines and lake sediments surrounding Issyk Kul, the world's second largest mountain lake, record fluctuating lake levels during Quaternary times. Together with bathymetric and geochemical data, these markers document alternating phases of lake closure and external drainage. The uppermost level of lake sediments requires a former damming of the lake's western outlet through the Boam gorge. We test previous hypothesised ice or landslide dam failures by exploring possible links between late Quaternary lake levels and outbursts. We review and recompile the chronology of reported changes in lake site, and offer new ages of abandoned shorelines using ¹⁴C in bivalve and gastropod shells, and plant detritus, as well as sand lenses in delta and river sediments using Infrared Stimulated Luminescence. Our dates are consistent with elevated lake levels between ~45 ka and 22 ka. Cosmogenic ¹⁰Be and ²⁶Al exposure ages of fan terraces containing erratic boulders (>3 m) downstream of the gorge constrain the timing of floods to 20.5–18.5 ka, postdating a highstand of Issyk Kul. A flow‐competence analysis gives a peak discharge of >10⁴ m³ s^–1 for entraining and transporting these boulders. Palaeoflood modelling, however, shows that naturally dammed lakes unconnected to Issyk Kul could have produced such high discharges upon sudden emptying. Hence, although our data are consistent with hypotheses of catastrophic outburst floods, average lake‐level changes of up to 90 mm yr^–1 in the past 150 years were highly variable without any outbursts, so that linking lake‐level drops to catastrophic dam breaks remains ambiguous using sedimentary archives alone. This constraint may readily apply to other Quaternary lakes of that size elsewhere. Nonetheless, our reconstructed Pleistocene floods are among the largest reported worldwide, and motivate further research into the palaeoflood hydrology of Central Asia. Copyright © 2017 John Wiley & Sons, Ltd.     

Identifying causes of ground-penetrating radar reflections using time-domain reflectometry and sedimentological analyses

Ground-penetrating radar (GPR) is a geophysical technique widely used to study the shallow subsurface and identify various sediment features that reflect electromagnetic waves. However, little is known about the exact cause of GPR reflections because few studies have coupled wave theory to petrophysical data. In this study, a 100- and 200-MHz GPR survey was conducted on aeolian deposits in a quarry. Time-domain reflectometry (TDR) was used to obtain detailed information on the product of relative permittivity (ɛ_r) and relative magnetic permeability (μ_r), which mainly controls the GPR contrast parameter in the subsurface. Combining TDR data and lacquer peels from the quarry wall allowed the identification of various relationships between sediment characteristics and ɛ_rμ_r. Synthetic radar traces, constructed using the TDR logs and sedimentological data from the lacquer peels, were compared with the actual GPR sections. Numerous peaks in ɛ_rμ_r, which are superimposed on a baseline value of 4 for dry sand, are caused by potential GPR reflectors. These increases in ɛ_rμ_r coincide with the presence of either organic material, having a higher water content and relative permittivity than the surrounding sediment, or iron oxide bands, enhancing relative magnetic permeability and causing water to stagnate on top of them. Sedimentary structures, as reflected in textural change, only result in possible GPR reflections when the volumetric water content exceeds 0·055. The synthetic radar traces provide an improved insight into the behaviour of radar waves and show that GPR results may be ambiguous because of multiples and interference.