On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry: Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron ⁵⁵Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10^− 9 mol/m² or 1.7 × 10^− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log K_Fe'W = 11.0 ± 0.3 m²/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 ⁻⁴–10^− 5 L/s and rate constants for association in the order of 10⁸ L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.     

Chalk shore platform erosion in the vicinity of sea defence structures and the impact of construction methods

Erosion of the intertidal chalk platform in the vicinity of groynes and seawalls is evident to the naked eye along many stretches of the engineered coastline of southeast England, leading to undermining and eventually failure of these structures. However, quantification of the magnitude and spatial extent of the erosion has been difficult to date because of a lack of data about the past elevation of the platform. The application of softcopy photogrammetry makes it possible to recreate past platform elevations from historic air photographs and to compare these with elevations from modern air photographs. Coastal sea defence structures have been installed along the chalk coast east of Brighton at various dates over the past 70 years. During this period, the construction methods have changed from predominantly manual labour to a reliance on heavy machines. The analysis of erosion patterns around structures built since the 1970s using heavy machinery show that surface lowering is 4 to 25 times greater in the vicinity of these structures than across the platform as a whole. In contrast, there is no similar pattern of increased erosion around structures built using predominantly manual labour in the 1930s. A four fold increase in average surface lowering is found also along a vehicle trackway that crosses the mid platform. Depressions developed by enhanced lowering in the front of seawalls generate their own dynamic of increased erosion by trapping pebbles and cobbles that enhance the abrasion of the chalk through bedload transport under standing waves in front of the walls.     

On the use of poorly soluble hygroscopic substances for modification of warm clouds and fogs

From analysis of the relationships between the equilibrium state of condensation nuclei and the relative humidity, a conclusion is made concerning the preferred use of poorly soluble substances for the generation of artificial condensation nuclei (ACN) designed for modification of warm clouds and fogs with the purpose of their dissipation and precipitation formation. The advantage of poorly soluble substances over commonly used soluble salts is that the finely dispersed part of the spectrum of the poorly soluble ACN does not deliquesce and so is not involved in the formation of cloud droplets. For experimental testing of the conclusions, preference was given to cement, whose main soluble substance is calcium oxide with a solubility of about 1 g/l. The spectrum of dispersed cement particles was measured and compared with the spectra of pyrotechnic flares widely used for modification at present. The process of formation of the cloud droplet spectra was simulated in the aerosol chamber of the Institute of Experimental Meteorology by decreasing the preliminarily generated excess pressure. It was found in these experiments that, compared to the spectra of particles formed on background condensation nuclei, the introduction of dispersed cement leads to the broadening of spectra and to a decrease in the concentration of droplets. Even at the early stage of condensation, droplets with radii of ∼20 μm appear. In this case, no “overseeding” phenomenon is observed, which, for soluble substances, manifests itself in an increase in the concentration of cloud droplets with a large ACN concentration. These effects indicate that, according to the existing concepts about the mechanism of warm-cloud modification with hygroscopic substances, the introduction of poorly soluble ACN (in particular, dispersed cement) below the base of cumulus clouds should stimulate coagulation processes and accelerate rain-formation processes. Considerations are given that the introduction of poorly soluble ACN into the already existing cumulus or stratocumulus clouds or fogs should also result in the acceleration of precipitation-formation processes or cloud dispersal. Comparison of cement powder with the well-known means of warm-cloud and fog modification is carried out. Original Russian Text ? N.P. Romanov, A.S. Drofa, N.S. Kim, A.V. Savchenko, G.F. Yaskevich, 2006, published in Izvestiya AN. Fizika Atmosfery i Okeana, 2006, Vol. 42, No. 1, pp. 80–91.     

Estimation of the long-term variability of hydrophysical characteristics of the Black Sea based on the assimilation of the climatic hydrological fields L and altimetry data

To study the long-term variability of the thermohaline and dynamic characteristics of the Black Sea, we use three versions of climatic fields, namely, the fields reconstructed in the model according to the old (1903–1982) and new (1903–2003) hydrological climatic data arrays of temperature and salinity and according to the data of satellite altimetry. The analysis of the altimetry-based climatic fields confirms the distinctions (established earlier according to the old and new data arrays) in the seasonal variability of the integral characteristics of temperature and salinity and in the structures of hydrophysical fields in the sea. It is shown that, in the winter-spring season, the thermohaline fields reconstructed according to the new and altimetry data arrays are characterized by a small elevation of the halocline (pycnocline) and the upper boundary of the cold intermediate layer. In all seasons, the altimetry-based surface geostrophic currents contain numerous mesoscale eddies with different signs of rotation. Moreover, in all seasons, the Rim Current reconstructed according to the altimetry data is characterized by a narrower jet almost along the entire its length. This jet is especially intense near the coasts of West Anatolia. __________ Translated from Morskoi Gidrofizicheskii Zhurnal, No. 4, pp. 3–17, July–August, 2006.     

Measurements of higher harmonic wave forces on a vertical truncated circular cylinder

Wave forces on a vertical truncated circular cylinder in Stokes waves with the wave slopes ranging from 0.06 to 0.24, are measured in a wave tank. The higher harmonic wave forces are compared with the available values from theories of the FNV (Faltisen–Newman–Vinje) model and Varyani solution. The first harmonic horizontal forces measured are much larger than the theoretical values from the FNV model, while the first harmonic vertical forces are well predicted by the Varyani theory. It was also found that the FNV model significantly overpredicts the second harmonic horizontal forces in high frequency waves, but under predicts the third harmonic forces. The differences between the actual measurement and the theory, in the second and third harmonic horizontal forces, become smaller at low wave frequencies as the wave slope increases. In addition, the transverse instabilities in the incoming waves with high wave slope were observed, which is due to the nonlinear modulation. Measurements were, thus, carried out before the instability occurred.     

Local remineralization patterns in the mesopelagic zone of the Eastern North Atlantic, off the NW Iberian Peninsula

The short-time-scale variability of the remineralization patterns in the domain of Eastern North Atlantic Central Waters (ENACW) off the NW Iberian Peninsula is studied based on biogeochemical data (oxygen, nutrient salts, total alkalinity, pH, dissolved organic matter and fluorescence of dissolved humic substances) collected weekly between May 2001 and April 2002. The temporal variability of inorganic variables points to an intensification of remineralization during the summer and autumn, with an increase of nutrients, total inorganic carbon and fluorescence and a decrease of oxygen. During the subsequent winter mixing, there is a biogeochemical reset of the system, with lower nutrients, total inorganic carbon and fluorescence and higher oxygen. In contrast to inorganic variables, the levels of dissolved organic matter in the ENACW seem to respond to short-term events probably associated with fast sinking particles, where solubilisation of organic matter prevails over remineralization. Applying a previously published stoichiometric model, we observed a vertical fractionation of organic-matter remineralization. Although there is a preferential remineralization of proteins and P compounds in the entire domain of ENACW, the percentage was higher in the upper ENACW (σ<27.10 kg/m³) than in the lower; the percentage of N and P compounds in the oxidised organic matter was >80% for the upper ENACW and 63% for the lower. Likewise, the redissolution of calcareous structures contributes about 6% and 13% to the carbon regenerated in the upper and lower layers of ENACW, respectively.     

High-resolution sediment echosounding off Peru: Late Quaternary depositional sequences and sedimentary structures of a current-dominated shelf

About 6000 km of both bathymetric and high-resolution acoustic profiles were acquired on the shelf and upper slope offshore Peru between 9° S and 14° S. Two new sediment echosounder systems – SEL-96 and SES-2000DS – provided details of the sedimentary structures of the Quaternary sequences within the Sechura-Salaverry, Huacho and Pisco Basins. To a great extent, the poleward undercurrent determines the distribution of sediments. The undercurrent has generated numerous erosional unconformities, it has winnowed hardgrounds and has created mudwaves common between 250 m and 400 m water depth. Distinct subbottom reflectors within sedimentary units represent hiatuses due to periods of intensified winnowing or non-deposition. Erosional unconformities usually marked by pronounced reflectors suggest shifts of the undercurrent system related to climatic changes and eustatic variations of sea level. On a larger scale, the stacked prograding depositional sequences reflect the sea-level cycles of the Middle Pleistocene to the Holocene. Based on the stratigraphy of our piston cores and that of Ocean Drilling Program (ODP) Site 680, the depositional sequences limited by extended unconformities were assigned to oxygen isotope stages 1 to 7. Other sedimentary structures are small straight channels that were conduits for downslope sediment transport. Deformed sediments associated with synsedimentary normal faults result from creep movements indicating beginning slope failure.     

Dynamic evolution of the 1997–1999 El Niño–La Niña cycle in the southern California Current System

The development of the strongest El Niño event on record in the equatorial Pacific in 1997–1998 and the rapid transition to strong La Niña conditions in 1998–1999 had a large impact on the physical and biological environment of the West Coast. We investigate the evolution of the physical structure and circulation dynamics of the southern California Current System (CCS) during this period based on hydrographic data collected on 25 cruises over a 45-month period (February 1996–October 1999). The El Niño period was characterized by a significant increase in dynamic height, extreme water mass characteristics, a strengthening and broadening of the poleward nearshore flow, and a temporary reversal of net alongshore transport. By early 1999, conditions in the CCS had reversed. The data suggest that remotely driven forcing (propagating oceanic waves) contributed to the anomalies observed during the El Niño period, while the cool-water conditions of 1999 were most likely a result of anomalous local atmospheric forcing.