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.     

Seasonal evolution of the transverse thermohaline asymmetry in the Ria de Pontevedra (northwestern Spain)

A quasi-permanent transverse asymmetry in the thermohaline properties of the Ria de Pontevedra (northwestern Spain) was measured from October 1997 to October 1998 during 23 cruises. On average, the density increased form north to south. This asymmetry was maintained by salinity during the wet season, and by salinity and temperature during the dry season. The density difference between coasts (Δσ_t = σ_tsouth − σ_tnorth) and the river discharge were positively correlated (correlation coefficient, approximately 0.6) throughout the year. The density difference was negatively correlated with the upwelling index during the wet season (correlation coefficient, approximately −0.45) and positively correlated during the dry season (correlation coefficient, approximately 0.55).     

Rock magnetic records of the sediments of the eastern Arabian Sea: Evidence for late Quaternary climatic change

Rock-magnetic measurements along with grain size, acid-insoluble residue (AIR), organic carbon (OC), CaCO₃ and δ¹⁸O of the planktonic foraminifers of the sediments were determined for 15 gravity cores recovered from the western continental margin of India. Magnetic susceptibility (MS) values in the surficial sediments reflect the land-derived input and, in general, are the highest in terrigenous sediment-dominated sections of the cores off Saurashtra–Ratnagiri, followed by the sediments off Indus–Gulf of Kachchh and then Mangalore–Cape Comorin.

The down-core variations in mineral magnetic parameters reveal that the glacial sediments off the Indus are characterized by low MS values/S-ratios associated with high AIR-content, low OC/CaCO₃ contents and relatively high δ¹⁸O values, while those off SW India are characterized by low MS values/high S-ratio% associated with low AIR content, and relatively high OC, CaCO₃ and δ¹⁸O values. Conversely, the Early Holocene sediments of all cores are characterized by high MS values/S-ratio% associated with high AIR content, low OC, CaCO₃ contents and gradually decreased δ¹⁸O values. These results imply that during the Last Glacial Maximum (LGM), the cores off northwestern India received abundant continental supply leading to the predominance of eolian/fluvial sedimentation. In the SW region the influence of hinterland flux is less evident during this period, but convective mixing associated with the NE monsoon resulted in increased productivity. During the early Holocene intense SW monsoon conditions resulted in high precipitation on land, which in turn contributed increased AIR content/MS values in the continental margin sediments. A shallow water core off Kochi further suggests that the intense SW monsoon conditions prevailed until about 5 ka. The late Holocene organic-rich sediments of the SW margin of India were, however, subjected to early diagenesis at different intervals in the cores. Therefore, caution is needed when interpreting regional climatic change from down-core changes in sediment magnetic properties.     

Transformation of the Level of Barotropic Ocean under an Elliptic Region of Disturbances of a Baric Field

We study elevations of the level of a homogeneous ocean caused by a large-scale elliptic anomaly of the field of atmospheric pressure and determine the conditions under which Earth's rotation and the asymmetry of the region of disturbances of the baric field lead to significant deviations of the ocean level from its values given by the law of inverted barometer. Our investigation is based on the numerical analysis of the integral solution of the linear problem. It is shown that the deviations from the law of inverted barometer are especially pronounced in shallow-water regions, at high latitudes, and for strongly asymmetric regions of disturbances of atmospheric pressure.     

Wave run-up and overtopping on smooth and rough slopes of coastal structures

A series of hydraulic model tests has been carried out in a glass wave flume to investigate the influences of wave height, wave period, wave steepness, surf similarity parameter, roughness, layer thickness and porosity on wave run-up and overtopping of 1:2 sloped impermeable and permeable breakwaters fronted by a 1:10 gentle, smooth beach slope. The analysis of results involves the correlation between the overtopping energy transfer with the relative wall height and the relationship between wave run-up and overtopping rate. Further, measured wave run-up and overtopping rates are compared with the results given in the Shore Protection Manual (1984), Automated Coastal Engineering System (1992)and results of other investigators.     

Modeling of coupled tide–wave–surge process in the Yellow Sea

A coupled wave–tide–surge model has been developed in this study in order to investigate the effect of the interactions among tides, storm surges, and wind waves. The coupled model is based on the synchronous dynamic coupling of a third-generation wave model, WAM cycle 4, and the two-dimensional tide–surge model. The surface stress, which is generated by interactions between wind and wave, is calculated by using the WAM model directly based on an analytical approximation of the results using the quasi-linear theory of wave generation. The changes in bottom friction are created by the interactions between waves and currents and calculated by using simplified bottom boundary layer model. In consequence, the combined wave–current-induced bottom velocity and effective bottom drag coefficient were increased in the shallow waters during the strong storm conditions.     

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.     

Seasonal variations of alkenones and U37 in the Chesapeake Bay water column

Alkenone unsaturation indices (U^K₃₇ and U^K′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between U^K₃₇ (and U^K′₃₇) values and temperature, and a significant negative correlation between U^K₃₇ (and U^K′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. U^K₃₇ relationships (U^K₃₇=0.018 (T)−0.162, R²=0.84, U^K′₃₇=0.013 (T)−0.04, R²=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index U^K′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the U^K₃₇ vs. temperature slope, or nutrient levels are the main controller of the U^K₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.     

Management of a shallow temperate estuary to control eutrophication: The effect of hydrodynamics on the system’s nutrient loading

The Mondego estuary, a shallow warm-temperate intertidal system located on the west coast of Portugal, has for some decades been under severe ecological stress, mainly caused by eutrophication. Water circulation in this system was, until 1998, mainly dependent on tides and on the freshwater input of a small tributary artificially controlled by a sluice. After 1998, the sluice opening was effectively minimised to reduce the nutrient loading, and the system hydrodynamics improved due to engineering work in the upstream areas. The objective of the present study was to evaluate the effect of the mitigation measures implemented in 1998. Changes to the hydrodynamics of the system were assessed using precipitation and salinity data in relation to the concentrations of dissolved inorganic nutrients, as well as the linkage between dissolved N:P ratios and the biological parameters (phytoplankton chlorophyll a concentrations, green macroalgal biomass and seagrass biomass). Two distinctive periods were compared, over a ten year period: from January 1993 to January 1997 and from January 1999 until January 2003. The effective reduction in the dissolved N:P atomic ratio from 37.7 to 13.2 after 1998 is a result of lowered ammonia, but not the oxidised forms of nitrogen (nitrate plus nitrite), or increased concentrations of dissolved inorganic phosphorus. Results suggest that the phytoplankton is not nutrient limited, yet maximum and mean biomass of green macroalgae was reduced by one order of magnitude after the mitigation measures. This suggests that besides lowering the water residence time of the system, macroalgal growth became nitrogen limited. In parallel to these changes the seagrass-covered area and biomass of Zostera noltii showed signs of recovery.