An optimized method for automated analysis of algal pigments by HPLC

A recent development in algal pigment analysis by high-performance liquid chromatography (HPLC) is the application of automation. An optimization of a complete sampling and analysis protocol applied specifically in automation has not yet been performed. In this paper we show that automation can only be successful if the various methodological aspects of the sampling and analysis protocol are considered in coherence. We introduce an optimized protocol that involves freeze-drying of the sample, subsequent extraction in 90% acetone and the application of water-packing during analysis. The method was evaluated on both natural plankton populations and a broad spectrum of microalgal cultures: Thalassiosira weisflogii (Bacillariophyceae), Emiliania huxleyi (Prymnesiophyceae), Phaeocystis globosa and Phaeocystis antarctica (Prymnesiophyceae) and Pyramimonas sp. (Prasinophyceae). Whereas pigment extracts were unstable in methanol, with recorded chlorophyll a losses from 10% to 60% per day, pigment degradation rates in acetone were generally less than 1% over 18 h storage in the autosampler (4 °C). In addition, it was found that the extraction efficiency of acetone significantly increased upon freeze-drying prior to extraction. Increases as high as 50–60% were measured in P. antarctica. The application of water-packing of the sample during injection resulted in improved peak shape and peak separation, without diluting the pigment concentrations. Automation is especially beneficial for application in the field, when mixed algal assemblages and low biomass put a high demand on the sensitivity as well as reproducibility of the method.     

Multi-decadal synthesis of benthic–pelagic coupling in the western arctic: Role of cross-shelf advective processes

Using geographic information systems (GIS) software and geostatistical techniques, we utilized three decades of water-column chlorophyll a data to examine the relative importance of autochthonous versus allochthonous sources of reduced carbon to benthic communities that occur from the northern Bering to the eastern Beaufort Sea shelf. Spatial trend analyses revealed areas of high benthic biomass (>300 g m⁻²) and chlorophyll (>150 mg m⁻²) on both the southern and northern Chukchi shelf; both areas are known as depositional centers for reduced organic matter that originates on the Bering Sea shelf and is advected northward in Anadyr and Bering shelf water masses. We found a significant correlation between biomass and chlorophyll a in the Chukchi Sea, reflective of the strong benthic–pelagic coupling in a system that is utilized heavily by benthic-feeding marine mammals. In contrast, there was no significant correlation between biomass and chlorophyll in the Beaufort Sea, which by comparison, is considerably less productive (biomass and chlorophyll, <75 g m⁻² and <50 mg m⁻², respectively). One notable exception is an area of relatively high biomass (50–100 g m⁻²) and chlorophyll (80 mg m⁻²) near Barter Island in the eastern Beaufort Sea. Compared to other adjacent areas in the Beaufort Sea, the chlorophyll values in the vicinity of Barter Island were considerably higher and likely reflect a long-hypothesized upwelling in that area and close coupling between the benthos and autochthonous production. In the Bering Sea, a drop in benthic biomass in 1994 compared with previous measurements (1974–1993) may support earlier observations that document a decline in biomass that began between the 1980s and 1990s in the Chirikov Basin and south of St. Lawrence Island. The results of this study indicate that the benthos is an excellent long-term indicator of both local and physical advective processes. In addition, this work provides further evidence that secondary production on arctic shelves can be significantly augmented by reduced carbon advected from highly productive adjacent shelves.     

Constraining the origin and evolution of confined turbidite systems: southern Cretan margin,Eastern Mediterranean Sea (34°30–36°N)

Bathymetric, 9.5-kHz long-range sidescan sonar (OKEAN), seismic reflection and sediment-core data are used in the analysis of two tectonic troughs south of Crete, Eastern Mediterranean Sea. Here, up to 1.2 s two-way travel time (TWTT) of strata have accumulated since the Middle Miocene in association with extension in the South Aegean region. The study area comprises >100-km- long by >25-km-wide basins filled by sediments subdivided into two seismic units: (1) an upper Unit 1 deposited in sub-basins which follow the present-day configuration of the southern Cretan margin; (2) a basal Unit 2, more than 500 ms (TWTT) thick, accumulated in deeper half-graben/grabens distinct from the present-day depocentres. Both units overlap a locally stratified Unit 3 comprising the pre-Neogene core complex of Crete and Gavdos. In this work, the interpreted seismic units are correlated with the onshore stratigraphy, demonstrating that denudation processes occurring on Crete and Gavdos in response to major tectonic events have been responsible for high sedimentation rates along the proximal southern Cretan margin. Consequently, topographically confined sedimentary units have been deposited south of Crete in the last 12 Ma, including turbidites and other mass-flow deposits fed by evolving transverse and axial channel systems. Surface processes controlling facies distribution include the direct inflow of sediment from alluvial-fan systems and incising mountain rivers onto the Cretan slope, where significant sediment instability processes occur at present. In this setting, seismic profiles reveal eight different types of stratigraphic contacts on basin-margin highs, and basinal areas show evidence of halokinesis and/or fluid escape. The acquired data also show that significant changes to the margin’s configuration occurred in association with the post-Alpine tectonic and eustatic episodes affecting the Eastern Mediterranean.     

A new method for the generation of second-order random waves

In order to prevent the generation of spurious free sub- and superharmonics of random waves in a laboratory channel, the control signal for the wave board has to be derived according to a higher-order wave theory. An expression for this control signal has been derived with the perturbation method of multiple scales. It is much less complex and requires less computation time than the expressions obtained from the full second-order theory. The new method for second-order subharmonics was verified experimentally for waves with bichromatic and continuous first-order spectra. The data were analysed with the complex-harmonic principal-component analysis to reduce the influence of noise.     

Measurement of the redox speciation of iron in seawater by catalytic cathodic stripping voltammetry

Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (Fe_R) in the absence and presence of 2 μM Dp, Fe_R being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H₂O₂ and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for Fe_R. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for Fe_R, iron(III) and iron(II), respectively, using a 60 s deposition time.The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of Fe_R ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column.     

Risk of dike failure due to flow slides

Flow slides may affect the stability of dikes. A flow slide is an instability of a submerged slope caused by liquefaction of loose, (medium) fine sand. Whether a flow slide will occur depends on the properties of the sand, which are a function of its density, and the geometry of the slope, as determined by wave and current induced scour and sedimentation. The influence of sand properties and the geometry parameters on the risk of flow slides are discussed. The application of a flow slide prediction method to an example and a risk analysis is briefly discussed.     

Mechanisms controlling the temporal variation of the sea ice edge in the Southern Ocean

This paper examines the mechanism controlling the short time-scale variation of sea ice cover over the Southern Ocean. Sea ice concentration and ice velocity datasets derived from images of the Defense Meteorological Satellite Program (DMSP) Special Sensor Microwave Imager (SSM/I) are employed to reveal this mechanism. The contribution of both dynamic and thermodynamic processes to the change in ice edge location is examined by comparing the meridional velocity of ice edge displacement and sea ice drift. In the winter expansion phase, the thermodynamic process of new ice production off the ice edge plays an important role in daily advances of ice cover, whereas daily retreats are mostly due to southward ice drift. On the other hand, both advance and retreat of ice edges in the spring contraction phase are mostly caused by the dynamic process of the ice drift. Based on the above mechanism and the linear relation between the degree of ice production at the ice edge and northward wind speed, the seasonal advance of ice cover can be roughly reproduced using the meridional velocity of ice drift at the ice edge.     

The Levant Slumps and the Phoenician Structures: collapse features along the continental margin of the southeastern Mediterranean Sea

Two distinct series of slumps deform the upper part of the sedimentary sequence along the continental margin of the Levant. One series is found along the base of the continental slope, where it overlies the disrupted eastern edge of the Messinian evaporites. The second series of slumps transects the continental margin from the shelf break to the Levant Basin. It seemed that the two series were triggered by two unrelated, though contemporaneous, processes. The shore-parallel slumps were initiated by basinwards flow of the Messinian salt, that carried along the overlying Plio-Quaternary sediments. Seawater that percolated along the detachment faults dissolved the underlying salt to form distinctly disrupted structures. The slope-normal slumps are located on top of large canyons that cut into the pre-Messinian sedimentary rocks. A layer of salt is found in the canyons, and the Plio-Quaternary sediments were deposited on that layer. The slumps are bounded by large, NW-trending faults where post-Messinian faulted offset was measured. We presume that the flow of the salt in the canyons also drives the slope-normal slumps. Thus thin-skinned halokynetic processes generated the composite post-Tortonian structural patterns of the Levant margin. The Phoenician Structures are a prime example of the collapse of a distal continental margin due to the dissolution of a massive salt layer.     

Transient biouptake flux and accumulation by microorganisms: The case of two types of sites with Langmuir adsorption

The uptake of a chemical species by an aquatic microorganism is modelled considering two kinds of sites where Langmuirian adsorption is followed by first order internalisation kinetics. Simpler models, such as only one internalisation route (while most of the adsorption takes place on non-internalising sites) or a linear isotherm for adsorption on one or both sites, become limiting cases of this double-Langmuirian model. The model considers the sites located on the spherical (or semi-spherical) surface of the organism, and takes diffusion from the medium into explicit account. The numerical solution for the internalisation flux shows a maximum. We provide an estimate for the time needed to reach a certain proximity to steady state. The transient solution confirms that the analytical expressions for the steady-state flux are usually valid and that the accumulated amounts reflect the impact of the short-time uptake. The Instantaneous Steady-State Approximation (ISSA), where an intercept of the linear regression of accumulated amount as a function of time is interpreted as an adsorbed amount, can be critically assessed with the transient numerical code for two cases: (i) when the total burden of metal on the cell is the input data and (ii) when an extraction procedure provides further information on the adsorbed and internalised amount.