The estimation of acid dissociation constants in seawater media from potentionmetric titrations with strong base. I. The ionic product of water — Kw

The various assumptions implicit in the calculation of acid dissociation constants (based on ionic medium standard states) from potentiometric titrations using a cell with liquid junction (i.e. a pH measuring cell) have been examined. It was concluded that results can be obtained having an accuracy commensurate with the experimental precision. It has been shown that although the precise composition of the medium is a function of the hydrogen ion concentration (because of the protolytic nature of some of the ions in the media, e.g., sulphate and fluoride), the effect of such variations in the medium composition can be compensated for when defining the activity of hydrogen ion on an ionic medium standard state by defining the concentration of hydrogen ion as:

where β_HSO4 and β_HF are the relevant association constants and S_T and F_T are the total concentrations of sulphate and fluoride, respectively.This approach was used to obtain values for the ionic product of water (K_W) in artificial seawater media at various temperatures and ionic strengths. These were fitted to give the equation (molal concentration units):

$\text{pK}{}_{\mathrm{w}}\text{=}\text{3441.0}\text{T}\text{+2.256-0.7091}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(}\text{rms deviation 0.01}\text{)}$

where I is the formal ionic strength of the artificial seawater medium and T is the absolute temperature. The values obtained are in reasonable agreement with those found by previous workers.     

Assessment of imposex in the common whelk, Buccinum undatum (L.) from the Eastern Scheldt, The Netherlands

Several cruises were carried out on the Eastern Scheldt between September 1992 and March 1995 to study the frequency and appearance of imposex in the common whelk, Buccinum undatum L. Incidences of imposex were always > 90%. For the first time several stages of imposex in Buccinum undatum are reported. The evolution of imposex in the whelk seems to follow a similar route as in Hinia reticulata belonging to the same superfamily (Buccinacea). Tissue organotin concentrations of animals collected in February 1995 showed the highest organotin concentrations in the digestive gland and lowest in the foot of the animals. Concentrations of phenyltin compounds (up to 625 ngSn/g DW) were much higher than those of butyltin compounds (up to 40 ngSn/g DW).     

Deep tow studies of the Tamayo transform fault

The Tamayo transform fault occurs at the north end of the East Pacific Rise where it enters the Gulf of California. The two deep-tow surveys reported here show that the transform fault zone changes significantly as a function of distance from the spreading center intersections. At site 1, near the intersection, one side of the fault is young and the fault zone is narrow and well-defined. Strike slip occurs in a zone approximately 1-km wide suggesting a correspondingly narrow zone of decoupling between the Pacific and North American plates. On the young side of the strike-slip zone, normal faults occur along shear zones which are 45°–50° oblique to the transform strike. They occur parallel to the short axis of the strain ellipse for transform fault strain here, i.e., perpendicular to the least compressive stress. The transform walls are formed by normal faulting as has been pointed out in previous detailed surveys. Here, however, the age contrast of 2.5 m.y. across the transform valley is apparent in the morphology of the normal fault scarps. While the scarps are steep and well-defined on the young side, the scarps on the older side have gradual 10°–30° slopes and appear to be primarily talus ramps. Apparently, the scarps have been tectonically eroded by continued strike slip activity after the initial stages of normal faulting. Thus, transform valleys should be quite asymmetric in cross-section where there is a significant age contrast and one side is less than approximately 0.5 m.y. old. Also, along older sections of the transform valley walls, normal faulting may not be at all obvious due to degradation of the scarps by tectonic erosion. This phenomenon makes the likelihood of transform faults providing windows into the oceanic crust most unlikely except in special cases.The picture of transform deformation is more complex at site 2 in the central portion of the fault where both sides of the fault are greater than 1 m.y. old. Here the transform valley is wider (25–30 km as opposed to 2–5 km). There is no clear simple zone of strike slip tectonics. In fact, the only clear evidence for deformation is the intrusion of magmatic or serpentinite diapirs through the sediments of the transform valley floor. The diapirs have deformed the turbidite layers flooring the valley and in one carefully studied case the turbidite sequence has been uplifted, perched atop the diapir. The pattern of deformation on this outcropping diapir shows radial and concentric fractures which can be modeled by a vertical intrusion circular in plan view. Magnetic studies limit the possible composition to basalt or serpentinite. A 60-km-long median ridge is also likely to be the product of intrusion along the transform fault. The survey at site 2 pointed out the importance of vertical tectonics in the transform valley floor and in particular the importance of diapiric intrusions of either basaltic or serpentinite composition.Based on initial boundary conditions and present tectonic elements in the Tamayo fault zone, a possible history of the mouth of the Gulf of California is outlined. The median ridge was emplaced starting approximately 0.8 m.y. ago by regional extension across the transform fault, the result of leaky transform faulting. The diapirs occur along a possible relay zone of extension midway along the fault which began approximately 0.15 m.y. ago. The extension in this case is parallel to the trend of the transform fault, is still occurring at present, and may evolve into a true spreading center.Contribution of the Scripps Institution of Oceanography, new series.     

Vibrations of a simply supported plate carrying an elastically mounted concentrated mass

A large number of papers and technical reports are available on the technically important problem of structural elements executing transverse vibrations and carrying concentrated masses. In general it is assumed that the attachment is perfectly rigid. On the other hand, a rather limited amount of published work is available when the mass is elastically connected to the structure. The system then exhibits a more complex behavior than in the case of rigid attachment. The present study deals with the solution of the title problem using the well-known normal mode, sinusoidal eigenfunction expansions.     

Unusual large-scale phytoplankton blooms in the equatorial Pacific

Unusual large-scale accumulations of phytoplankton occurred across 10,000 km of the equatorial Pacific during the 1998 transition from El Niño to La Niña. The forcing and dynamics of these phytoplankton blooms were studied using satellite-based observations of sea surface height, temperature and chlorophyll, and mooring-based observations of winds, hydrography and ocean currents. During the bloom period, the thermocline (nutricline) was anomalously shallow across the equatorial Pacific. The relative importance of processes that enhanced nutrient flux into the euphotic zone differed between the western and eastern regions of the blooms. In the western bloom region, the important vertical processes were turbulent vertical mixing and wind-driven upwelling. In contrast, the important processes in the eastern bloom region were wave-forced shoaling of nutrient source waters directly into the euphotic zone, along-isopycnal upwelling, and wind-driven upwelling. Advection by the Equatorial Undercurrent spread the largest bloom 4500 km east of where it began, and advection by meridional currents of tropical instability waves transported the bloom hundreds of kilometers north and south of the equator. Many processes influenced the intricate development of these massive biological events. Diverse observations and novel analysis methods of this work advance the conceptual framework for understanding the complex dynamics and ecology of the equatorial Pacific.     

Beach and dune erosion during storm surges

This paper presents the set-up and results of an extensive research programme concerning the erosion of coastal dunes during storm surges. A large number of two-dimensional and three-dimensional mobile-bed model tests has been carried out to investigate the process of dune erosion. The state of art after a series of small-scale tests is summarized. Attention is focussed on large-scale tests carried out in the Delta Flume with random waves up to 2 m significant height. Sediment concentration and orbital velocity measurements are discussed. The large-scale tests have confirmed the validity of a modelling technique based on the dimensionless fall velocity parameter H/Tw. The model results are being applied to check the safety of existing coastal dunes as a water-retaining structure that has to protect the major part of the Netherlands from inundation during storm surges.     

Spatial and temporal variability of the ratios between the nitrate and phosphate concentrations in the Sea of Okhotsk

The relation between the nitrate and phosphate concentrations in the Sea of Okhotsk and the bordering waters of the Pacific Ocean were studied. The surveys were carried out in the autumn, spring, and summer of 2001–2002. For the deepwater part of the sea, the relation [NO^? ₃] = ((14.88 ± 0.07) × [PO^3? ₄] ? 5.46 ± 0.17) was found. The coefficients in the equation given are statistically different from those in the similar equation for the Pacific waters: [NO^? ₃] = (16.05 ± 0.15) × [PO^3? ₄]-(7.23 ± 0.36). In the northern part of the sea; on the shelf; in the slope area; and, especially, in the deep waters of the TINRO Depression, the linear dependence between the phosphate and nitrate concentrations was distorted. This feature was described in terms of nitrate deficiency. The maximum values of this deficiency were found in the near-bottom waters. The principal processes that might cause the nitrate deficiency were considered: the difference in the oxidation rates of the nitrogen and phosphorus organic compounds, the matter transfer between the continent and the sea, the different efficiency of the biogenic burial of nitrogen and phosphorus in the bottom sediments, and the denitrification in the upper layer of the bottom sediments. It was shown that the most probable cause of the nitrate deficiency was the denitrification. The loss of inorganic nitrogen owing to the supply of the waters of the Sea of Okhotsk to the Pacific Ocean was estimated as ～2.5 × 10¹¹ mol N/year.