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.     

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.     

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.     

Nutrient variability during El Niño 1997–98 in the California current system off central California

Nutrient conditions off central California during the 1997–98 El Niño are described. Data were collected on 11 cruises from March 1997 to January 1999 along a hydrographic section off central California, as well as every two weeks at a coastal station in Monterey Bay. Perturbations associated with El Niño are shown as anomalies of thermohaline and nutrient distributions along this section. The anomalies were obtained by subtracting seasonal averages for the period from April 1988 to April 1991 from the 1997–98 observations. The first indications of El Niño conditions (high sea levels) were observed at Monterey between late May and early June 1997, but the coastal nutricline did not begin to deepen until August 1997. It reached maximum depth of 130 dbar in January 1998 at the time that maximum sea level anomalies were observed. During this period: (1) the highest subsurface temperature anomalies coincided with subsurface nutrient anomaly minima at the depth of the pycnocline; (2) southern saline and nutrient-poor waters occupied the upper 80 dbar of the water column along the entire section; and (3) nitrate levels were close to zero in the euphotic zone, collapsing the potential new primary production in the coastal domain. At the end of February 1998, the nutricline shoaled to 40 dbar at the coast although it remained anomalously deep offshore. Higher temperatures and lower nutrient levels were observed for the entire section through August 1998 although in contrast with the previous winter, there was a strong freshening mainly due to an onshore movement of subarctic waters.     

Environmental overview of Eckernförde Bay,northern Germany

This environmental overview of Eckernförde Bay (northern Germany) summarizes the results of previous studies relevant to the Office of Naval Research's Coastal Benthic Boundary Layer (CBBL) Baltic field exercise conducted during 1993–1994. Significant environmental characteristics include the following: (1) surface sediment distribution is related to water depth, dictated primarily by hydrodynamic reworking of older glacial deposits; (2) the origin and characteristics of small-scale sedimentary structures depend on storm-generated waves and currents; (3) the proximity of the sea surface and sediment —water interface results in a pelagic—benthic coupling that drives biogeochemical processes and produces organicrich, acoustically turbid sediments; and (4) the bay floor is complicated topographically by pockmarks and manmade sedimentary structures.