Concentrations of the elements Ag,Al, Ca,Cd, Cu,Fe, Mg,Mn, Pb and Zn,and the radionuclides 210Pb and 210Po in the digestive gland of the squid Nototodarus gouldi

Ag, Al, Ca, Cd, Cu, Fe, Mg, Mn, Pb and Zn concentrations and ²¹⁰Po and ²¹⁰Pb activities were measured in 26 specimens of the squid Nototodarus gouldi taken from the waters of Bass Strait in one jigging operation. All the elements show wide ranges in concentrations in specimens apparently subject to the same environmental conditions. Copper concentration was 27-1 200 μg/g, and ²¹⁰Po activity 4·8–24·2 Bq/g. The animal wet weights, the elements Ag, Al, Cd, Fe and Zn, and the radionuclide ²¹⁰Po have coefficients of variation in the range 40–60%; Ca, Mg and Mn show the smallest variability (CV = < 30%), and Cu the greatest (CV = 12%). Significant correlations (p < 0·001) were found between the following pairs of elements: Cd-Zn, Cd-Cu, Zn-Cu, Mg-Mn, Fe-Mn, Ca-Mg and Fe-²¹⁰Po.     

Quantitative phosphorus measurement: A field test procedure for archaeological site analysis at Piedras Negras,Guatemala

Currently there is a wide interest in the use of chemical analyses for the evaluation of anthropogenically altered soils and other archaeological deposits. Because soil phosphorus levels increase in areas of human habitation, and leave a permanent signature that can only be removed by erosion of the soil itself, phosphorus mapping has become a popular field procedure to indicate areas of habitation where overt evidence of ancient occupance is absent. We have developed a methodology to obtain accurate acid‐extractable phosphorus concentrations (mg/kg) in calcareous soils under the primitive field conditions of Piedras Negras, Guatemala. Predicated on Mehlich‐II acid extractant and colorimetric methods, this procedure processed 36 samples per hour at very low cost per sample. Based on eight replicate measurements of a group of samples, the coefficient of variation of the procedure was 8.3%. Subsequent analysis of 35 soil samples in a controlled laboratory revealed a moderate correlation of 0.44 between the Mehlich‐extractable phosphorus and total phosphorus. The correlation was 0.91 between the Mehlich procedure and Olsen bicarbonate extractable phosphorus, indicating that Mehlich‐based results are similar to those obtainable using a traditional extractable phosphorus method on soils of neutral to alkaline pH. There was a moderate correlation between Mehlich P and ring‐test rating (r = 0.42). The wider dynamic range of the Mehlich extraction, coupled with the use of a battery‐operated colorimeter, facilitated the finding of a refuse midden within an area of phosphate enriched soils. Further tests indicated that phosphorus concentrations measured in the field deviated by only 7% from those made under controlled laboratory conditions. © 2000 John Wiley & Sons, Inc.     

The calculation of estuarine turnover times using freshwater fraction and tidal prism models: A critical evaluation

Freshwater fraction and tidal prism models are simple methods for estimating the turnover time of estuarine water. The freshwater fraction method prominently features flushing by freshwater inflow and has sometimes been criticized because it appears not to include flushing by seawater, but this is accounted for implicitly because the average estuary salinity used in the calculation reflects all the processes that bring seawater into the estuary, including gravitational circulation and tidal processes. The model relies on measurable salinity differences among water masses and so must be used for estuaries with substantial freshwater inflow. Tidal prism models are based on flushing by flood tide inflow and ignore seawater inflow due to gravitational circulation. These models should only be applied to estuaries with weak or nonexistent gravitational circulation, which are generally those with little freshwater inflow. Using a framework that is less ambioguous and more directly applicable to the estimation of turnover times than those used previously, this paper critically examines the application of tidal prism models in well-mixed estuaries with complete tidal exchange, partial ebb return, or incomplete flood mixing and in partially mixed estuaries. Problems with self-consistency in earlier versions of these models also apply to the budgeting procedure used by the LOICZ (Land-Ocean Interactions in the Coastal Zone) program. Although freshwater fraction and tidal prism models are different approaches to estimating turnover times in systems with very different characteristics, consistent derivation shows that these models have much in common with each other and that they yield equivalent values that can be used to make comparisons across systems.     

Sedimentary iron monosulfides: Kinetics and mechanism of formation

The reaction between hydrous iron oxides and aqueous sulfide species was studied at estuarine conditions of pH, total sulfide, and ionic strength to determine the kinetics and formation mechanism of the initial iron sulfide. Total, dissolved and acid extractable sulfide, thiosulfate, sulfate, and elemental sulfur were determined by spectrophotometric methods. Polysulfides, S₄^2? and S₅^2?, were determined from ultraviolet absorbance measurements and equilibrium calculations, while product hydroxyl ion was determined from pH measurements and solution buffer capacity.Elemental sulfur, as free and polysulfide sulfur, was 86% of the sulfide oxidation products; the remainder was thiosulfate. Rate expressions for the reduction and precipitation reactions were determined from analysis of electron balance and acid extractable iron monosulfide vs time, respectively, by the initial rate method. The rate of iron reduction in moles/liter/minute was given by $\text{d(}\text{reduction}\text{Fe)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^{0.5}\text{(J}{}^{\mathrm{+}}\text{)}{}^{0.5}\text{A}{}_{\mathrm{FeOOH}}{}^1$ where S_t was the total dissolved sulfide concentration, (H⁺) the hydrogen ion activity, both in moles/ liter; and A_FeOOH the goethite specific surface area in square meters/liter. The rate constant, k, was 0.017 ± 0.002m^?2 min^?1. The rate of reduction was apparently determined by the rate of dissolution of the surface layer of ferrous hydroxide. The rate expression for the precipitation reaction was $\text{d(FeS)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^1\text{(H}{}^{\mathrm{+}}\text{)}{}^1\text{A}{}_{\mathrm{FeOOH}}{}^1$ where $\text{d(FeS)}\text{dt}$ was the rate of precipitation of acid extractable iron monosulfide in moles/liter/minute, and k = 82 ± 18 mol^?1l²m^?2 min^?1.A model is proposed with the following steps: protonation of goethite surface layer; exchange of bisulfide for hydroxide in the mobile layer; reduction of surface ferric ions of goethite by dissolved bisulfide species which produces ferrous hydroxide surface layer elemental sulfur and thiosulfate; dissolution of surface layer of ferrous hydroxide; and precipitation of dissolved ferrous specie and aqueous bisulfide ion.     

Correlation of210Po and210Pb enrichments in the sea-surface microlayer with neuston biomass

Samples of the surface microlayer, of bulk seawater from 20-cm depth and of the neustonic organisms inhabiting the top 5 cm of the sea were collected at regular intervals over a period of 17 months at a site 3 km off Monaco and analysed for the naturally occurring radionuclides²¹⁰Po and²¹⁰Pb. Enrichment of²¹⁰Po in the microlayer compared with the bulk seawater was always observed, and the degree of enrichment was found to be correlated significantly with the neuston biomass per unit volume. Enrichment of²¹⁰Pb in the microlayer was also observed, but only under the higher neuston biomass conditions. The²¹⁰Po:²¹⁰Pb ratio was always higher in the microlayer than in the bulk seawater. Additional information was obtained from²¹⁰Po measurements made on the bulk seawater in which the neuston had been collected and in which it had stood for periods of 2 to 4 h. These showed that the neuston lost²¹⁰Po to the water at a rate of about 1 pCi g^?1 dry biomass h^?1. A significant flux of²¹⁰Po from bulk seawater to the surface microlayer, and thence possibly to the atmosphere, is estimated. This flux is mediated by the biota, and will vary seasonally with the planktonic biomass. Under high biomass conditions a similar flux for²¹⁰Pb may also be significant. An association of²¹⁰Po with the organic cycle at the top of the sea, and with marine bacteria in particular, is suggested.     

The pressure quench formation of rapakivi texture

Chemical and textural data for rapakivi granites are combined with experimentally determined phase equilibria to provide constraints on the growth of mantled feldspars by a pressure quench mechanism. In water saturated melts of granitic composition the mantled texture develops in response to a decrease in pressure of as little as 1–0.5 kbar. In water undersaturated melts a similar mechanism is operable over a wider range of pressures and a restricted range of water contents. Water undersaturated granites containing 6–10 wt % water undergoing a change in pressure from 5–2 kbar will develop mantling as will a more calcic granodiorite containing 1–5wt% water undergoing a pressure change from 10-1 kbar. The mantling process is interpreted as a reflection of the reduction of pressure accompanying the emplacement of a magma.     

Matrix Diffusion Effects on Contaminant Migration from an Injection Well in Fractured Sandstone

Deep-well injection into fractured sandstone is an option for the disposal of contaminated mine dewatering discharge from an open pit uranium mine. As part of the assessment of potential contaminant migration from deep-well injection, the effect of matrix diffusion was evaluated. An analytical mathematical model was developed for the simulation of the radial movement of a contaminant front away from an injection point under steady flow conditions in a planar fracture with uniform properties. The model includes the effects of advection in the fracture, diffusion of contaminants from the fracture into the rock matrix, and equilibrium adsorption on the fracture surface as well as in the rock matrix. Effective diffusion coefficients obtained from laboratory experiments on 11 intact core samples varied from 3.4 × 10⁻⁸ to 3.2 × 10⁻⁷ cm²/s. Model simulations were made with diffusion coefficient values in this range and with single-fracture injection rates estimated from fracture frequencies in boreholes, and from bulk hydraulic conductivity values obtained from field tests. Because of matrix diffusion, the rate of outward movement of the front of the nonreactive contaminants from the injection well is much slower than the rate of water flow in the fractures. Simulations of the movement of contaminants that undergo adsorption indicate that even a small distribution coefficient for the rock matrix causes the contaminants to remain very close to the injection well during the one-year period. The results of the simplified model demonstrate that matrix diffusion is an important process that cannot be neglected in the assessment of a waste disposal scheme located in fractured porous rock. However, in order to make a definitive assessment of the capability of matrix diffusion and associated matrix adsorption to significantly limit the extent of contaminant migration around injection wells, it would be necessary to conduct field tests such as a preliminary or experimental injection.