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.     

Estimates of the characteristics of the horizontal turbulent exchange in the northwestern part of the Pacific Ocean

Estimates of the characteristics of the horizontal turbulent exchange (coefficients of horizontal exchange, scales of deviations of the velocity of geostrophic currents from the background flows, and horizontal scales of perturbations) in the upper ocean layer were obtained on the basis of the data of expeditions held in 1978 and 1980 in the northwestern part of the Pacific Ocean. It is shown that the characteristics of the horizontal turbulent exchange strongly depend on the structure of the background flows, and one of the causes of their variability is related to tropical cyclones. A tendency to a decrease (to different degrees) of the turbulent coefficients in the wake of a tropical cyclone is noted.     

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.     

Study of the mutual influence of the El Niño-Southern Oscillation processes and the North Atlantic and Arctic Oscillations

On the basis of the nonlinear techniques for the estimation of coupling between oscillatory systems from time series, we investigate the dynamics of climatic modes characterizing global and Northern Hemisphere (NH) processes. The North Atlantic Oscillation (NAO) and Arctic Oscillation indices and the El Niño-Southern Oscillation (ENSO) indices are analyzed in terms of the most reliable data from 1950 through 2004 and earlier data since the 19th century. These indices characterize changes in NH atmospheric pressure (specifically, sea-level pressure in the North Atlantic and NH extratropical latitudes as a whole) and in equatorial Pacific sea-surface temperature and sea-level pressure to which the strongest variations of global surface temperature and global climate on interannual time scales and of regional climatic anomalies in the NH are linked. The methods used are based on phase-dynamics modeling and nonlinear prediction models (a nonlinear version of Granger causality). From both methods and various ENSO indices, the inference about the ENSO effect on the NAO during the latter half of the 20th century and in the early 21st century is made with confidence probability of at least 0.95. The influence is characterized by a time delay of about two years. No inverse influence is found with a similar degree of reliability. Results of estimating the coupling between the ENSO and the NAO depend on the type of index that is used to describe the NAO. The ENSO effect on the NAO is detected with sufficient confidence when the NAO index is chosen to be a larger scale characteristic. However, when a more local index of the NAO is used, no statistically significant coupling to the ENSO is found. Increasing the length of the analyzed ENSO and NAO series (over more than 100 yr) does not lead to any more reliable detection of coupling. Analysis of the data for different time intervals during 1950–2004 has revealed a strengthening of the ENSO effect on the NAO, although this inference is not reliable.     

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.