On the sulphur chemistry of a super-anoxic fjord, Framvaren, South Norway

The concentrations of total carbonate (C_t), sulphate, sulphide, thiols and oxygen, the ratio between the stable sulphur isotopes ³⁴S and ³²S in sulphate and sulphide, and the density (used to calculate salinity) were determined on samples from the water column of Framvaren, a superanoxic fjord in southern Norway. From a depth of 18m (the oxic-anoxic boundary) the initial sulphate concentration, ([SO₄]_init), as calculated from salinity, is significantly higher than the sum of the measured sulphur species. This is attributed to a loss of sulphur from the water column. The amount of total carbonate produced, corrected for the initial concentration (C_t - 2.4 Sal/35) is found to be proportional to the amount of sulphate consumed, ([SO₄]_init - [SO₄]), according to the following relation C_t- 2.4 Sal/35 = 1.84 ([SO₄]_init - [SO₄]). Isotopic fractionation caused by bacterial sulphate reduction in the anoxic part of the water column produces sulphide with a δ³⁴S 40‰ lower than the δ³⁴S for sulphate at corresponding depths. The isotopic fractionation also results in δ³⁴S value for the remaining sulphate at depths below 80 m being considerably higher than the mean value for ocean water, which is close to + 20‰. The δ³⁴S values for sulphate at depths between 10 and 50 m were lower than + 20‰ which indicates oxidation of sulphide, which follows upon diffusion of sulphide from deeper parts of the water column and inflow of oxygenated seawater over the sill into the anoxic water of the fjord. A conclusive scenario of the Framvaren sulphur chemistry is presented.     

Analysis of Triphenyltin in Fish

A procedure to analyse triphenyltin and other organotins in fish tissues is described. The method consists of the following steps: homogenization of the fish, extraction by heating under reflux in a water/hexane mixture, centrifugation, separation of the hexane layer followed by reduction of the volume by evaporation, methylation of the organotin with a Grignard reaction, clean-up of the fish extract by column chromatography, and detection by gas chromatography with flame photometric detection. The extraction was carried out without adding acid or base to the aqueous phase, as the extraction efficiency was independent of pH. The methylation was successfully carried out in the fish extract. For clean-up of the fish extract a florisil column was used, from which the triphenylmethyltin was eluted with hexane. Using this method, triphenyltin has a recovery of 77 ± 10%, with a limit of detection of 0·8 ng/g for 0·1 g fish samples.     

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.     

Robust Range-Only Beacon Localization

In this paper, we present a system capable of simultaneously estimating the position of an autonomous underwater vehicle (AUV) and the positions of stationary range-only beacons. Notably, our system does not require beacon positions a priori, and our system performs well even when range measurements are severely degraded by noise and outliers. We present a powerful outlier rejection method that can identify groups of range measurements that are consistent with each other, and a method for initializing beacon positions in an extended Kalman filter (EKF). We have successfully applied our algorithms to real-world data and have demonstrated a simultaneous localization and mapping (SLAM) system whose navigation performance is comparable to that of systems that assume known beacon locations     

A community-wide intercomparison exercise for the determination of dissolved iron in seawater

The first large-scale international intercomparison of analytical methods for the determination of dissolved iron in seawater was carried out between October 2000 and December 2002. The exercise was conducted as a rigorously “blind” comparison of 7 analytical techniques by 24 international laboratories. The comparison was based on a large volume (700 L), filtered surface seawater sample collected from the South Atlantic Ocean (the “IRONAGES” sample), which was acidified, mixed and bottled at sea. Two 1-L sample bottles were sent to each participant. Integrity and blindness were achieved by having the experiment designed and carried out by a small team, and overseen by an independent data manager. Storage, homogeneity and time-series stability experiments conducted over 2.5 years showed that inter-bottle variability of the IRONAGES sample was good (< 7%), although there was a decrease in iron concentration in the bottles over time (0.8–0.5 nM) before a stable value was observed. This raises questions over the suitability of sample acidification and storage.     

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.