Chemical studies of copper-organic complexes isolated from estuarine waters using C18 reverse-phase liquid chromatography

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography employing C₁₈ Sep-Pak cartridges (Waters Associates). The cartridges were found to have a constant retention efficiency for processing ? 1-l volumes of seawater. Fractionation of the isolated material, by sequential elution of the Sep-Pak with water: methanol mixtures of increasing organic solvent concentration, yielded a fraction of the organic matter with a specific copper activity six times greater than the overall activity for the isolated DOM. Analysis of this fraction by high performance liquid chromatography suggested that the organic components are of intermediate polarity and have appreciable aromatic character.An investigation of the protonation characteristics of the isolated complexes indicated that most of the copper is associated with a broad range of acidic sites on the DOM. Analysis by electron paramagnetic resonance spectroscopy confirmed the organic association of the isolated copper and also suggested the presence of several types of binding sites which probably involve oxygen donor ligands.Studies of the exchange of ⁶⁴Cu with these binding sites on the isolated DOM indicated that 70% of the sites undergo rapid exchange with copper in seawater while 20% of these sites did not exchange in a 24-h time period.     

Exact formulas for approximating variogram function integrals

The application of regionalized variables requires the estimation of the variogram function and the evaluation of its integral. By representing the variogram by a polygonal function the integral may be easily approximated by closed form representations of polygonal integrals. This approach provides a basis for more extensive statistical evaluation not evident in existing approximation methods. This paper provides the closed form representations for two-dimensional variogram functions whose domain is represented by a finite collection of rectangles.     

Special features of cyclotron radiation in anisotropic plasmas

We analyze the special features of cyclotron radiation in four different modes radiated by a mildly relativistic electron current in an anisotropic plasma, taking into consideration that the radiation is transmitted along the group velocity, rather than the wave normal direction. A systematic series of numerical analysis is carried out, to demonstrate the characteristics of the focussing effect and Doppler effect of the radiation, arising from anisotropy. The parameters used pertain to plasmas and radiators of the types encountered in the terrestrial upper atmosphere and the solar corona.     

Towfish orientation and position estimation

The towfish location and orientation problems that arise in using side-scan sonar to detect objects on the sea bottom are treated separately. Data which locate the towfish relative to the ship are usually deteriorated by multipath receptions and other effects. In order to overcome this serious degradation in the location measurements, a modified Kalman filter is proposed. An estimate of the state transition matrix for this filter is derived, and a means of switching between two Kalman gains is suggested. The feasibility of the proposed filter is justified by a case study. Improved estimates of towfish pitch and heading measurements are obtained by a separate system employing model identification and subsequent Kalman filtering. Application of these methods to data from similar towed side-scan sonar systems should yield significant gains in object location accuracy     

Numerical solutions for flow in porous media

A numerical approach is proposed to model the flow in porous media using homogenization theory. The proposed concept involves the analyses of micro‐true flow at pore‐level and macro‐seepage flow at macro‐level. Macro‐seepage and microscopic characteristic flow equations are first derived from the Navier–Stokes equation at low Reynolds number through a two‐scale homogenization method. This homogenization method adopts an asymptotic expansion of velocity and pressure through the micro‐structures of porous media. A slightly compressible condition is introduced to express the characteristic flow through only characteristic velocity. This characteristic flow is then numerically solved using a penalty FEM scheme. Reduced integration technique is introduced for the volumetric term to avoid mesh locking. Finally, the numerical model is examined using two sets of permeability test data on clay and one set of permeability test data on sand. The numerical predictions agree well with the experimental data if constraint water film is considered for clay and two‐dimensional cross‐connection effect is included for sand. Copyright © 2003 John Wiley & Sons, Ltd.     

Metallothioneins and trace metals in the dogwhelk Nucella lapillus (L.) collected from Icelandic coasts

Different sizes of the dogwhelk Nucella lapillus were collected from eight locations along the southwest and north coasts of Iceland. Concentrations of total metallothioneins (MTs) and heavy metals (Cd, Cu, Cr, Mn, Ni, and Zn) were analysed using the silver saturation method and inductively coupled plasma-atomic emission spectrometry. The level of tributyltin (TBT) contamination was also assessed using imposex indices, the vas deferens stage index (VDSI) and relative penis size index (RPSI). Gufunes N. lapillus presented the highest values of VDSI (4.0) and RPSI (11.1), followed by Grenivík individuals (VDSI = 3.0; RPSI = 0.9), while the Strandakirkja population showed the lowest VDSI (0.3) and zero RPSI. At a standardised size (0.25 g dry soft-body weight), Grenivík N. lapillus exhibited significantly higher concentrations of all metals whereas overall metal concentrations were significantly lower in individuals from Strandakirkja and Garðskagi compared to other study sites. Partial correlation analyses with size correction indicated that MT concentrations were better correlated with Cd and Cu concentrations than with other metals. At the standard size, the pattern of MT concentrations in N. lapillus from different sites was, however, very different from those of metal profiles. Such discrepancies between the patterns of MT and metals in N. lapillus might be explained by the fact that MT induction could be influenced by various factors such as temperature, dietary metal intake, growth rate and co-existence of other MT-inducing chemicals.     

Toxicity of antifouling biocides to the intertidal harpacticoid copepod Tigriopus japonicus (Crustacea, Copepoda): effects of temperature and salinity

Intertidal harpacticoid copepods are commonly used in eco-toxicity tests worldwide. They predominately live in mid-high shore rock pools and often experience a wide range of temperature and salinity fluctuation. Most eco-toxicity tests are conducted at fixed temperature and salinity and thus the influence of these environmental factors on chemical toxicity is largely unknown. This study investigated the combined effect of temperature and salinity on the acute toxicity of the copepod Tigriopus japonicus against two common biocides, copper (Cu) and tributyltin (TBT) using a 2 × 3 × 4 factorial design (i.e. two temperatures: 25 and 35 °C; three salinities: 15.0‰, 34.5‰ and 45.0‰; three levels of the biocide plus a control). Copper sulphate and tributyltin chloride were used as the test chemicals while distilled water and acetone were utilised as solvents for Cu and TBT respectively. 96h-LC50s of Cu and TBT were 1024 and 0.149 μg l⁻¹ respectively (at 25 °C; 34.5‰) and, based on these results, nominal biocide concentrations of LC0 (i.e. control), LC30, LC50 and LC70 were employed. Analysis of Covariance using ‘concentration’ as the covariate and both ‘temperature’ and ‘salinity’ as fixed factors, showed a significant interaction between temperature and salinity effects for Cu, mortality increasing with temperature but decreasing with elevated salinity. A similar result was revealed for TBT. Both temperature and salinity are, therefore, important factors affecting the results of acute eco-toxicity tests using these marine copepods. We recommend that such eco-toxicity tests should be conducted at a range of environmentally realistic temperature/salinity regimes, as this will enhance the sensitivity of the test and improve the safety margin in line with the precautionary principle.     

On the relation between the amplitude of light and radial velocity variations of β Canis Majoris stars

The relation between the amplitude of light m and the amplitude of the radial velocity 2K for Canis Majoris stars is investigated. A linear relationship between m and 2K is found. However, the two stars BW Vul and Sco, which have the largest radial velocity variations, do not seem to share this relationship.     

Amplitude ratios of several groups of variable stars

The observed positions of classical cepheids, RR Lyrae stars, Scuti stars and dwarf cepheids in the logg-logT _e plane form a continuous sequence, thereby defining the location of maximum instability. The amplitude ratio (the ratio of radial velocity amplitude to light amplitude) is small for variables at the upper end of the instability strip and increases almost linearly towards the lower end of the strip. The theory of radial pulsation predicts the trend of this correlation.     

AGRICULTURAL DROUGHT ON SOUTH-CENTRAL PACIFIC ISLANDS *

A pilot study of spatial patterns of agricultural drought hazard in the south-central Pacific is presented. The durations of crop stress periods are estimated using a water balance approach. A rainfall approach is used to identify dry periods corresponding to different durations. Strong correlation between the results of the two methods indicates that monthly rainfall data are sufficient for estimating the patterns of agricultural drought hazard in the region. The simpler rainfall method is particularly useful for high islands where data required for the water balance approach are not sufficient to characterize the complex climatic patterns. Drought hazard is greatest in the eastern and southwestern parts of the study area. Great spatial variation in drought hazard is observed in a small area on the high islands of Western Samoa, where the range of values found within a few tens of kilometers is about the same as the range found across thousands of kilometers for low islands.