Solubility of hydrous ferric oxide and iron speciation in seawater

Iron solubility equilibria were investigated in seawater at 36.22‰ salinity and 25°C using several filtration and dialysis techniques. In simple filtration experiments with 0.05 μm filters and Millipore ultra-filters, ferric chlorides fluorides, sulfates, and FeOH²⁺ species were found to be insignificant relative to Fe(OH)₂⁺ at p[H⁺] = ?log [H⁺] greater than 6.0. Hydrous ferric oxide freshly precipitated from seawater yielded a solubility product of ${}^1\text{K}{}_{\mathrm{<mtext>so</mtext>}}\text{=}\text{[Fe}{}^{\mathrm{3+}}\text{][H}{}^{\mathrm{+}}\text{]}{}^{\mathrm{?3}}\text{= 4.7 · 10}{}^5$. Solubility studies based on the rates of dialysis of various seawater solutions and on the filtration of acidified seawater solutions indicated the existence of the Fe(OH)₃⁰ species. The formation constant for this species can be calculated as ${}^1\text{β}{}_3\text{=}\text{[Fe(OH)}{}_3{}^0\text{] [H}{}^{\mathrm{+}}\text{]}{}^3\text{/[Fe}{}^{\mathrm{3+}}\text{] = 2.4 · 10}{}^{\mathrm{?14}}$. The Fe(OH)₄^? species is present at concentrations which are negligible compared to Fe(OH)₂⁺ and Fe(OH)₃⁰ in the normal pH range of seawater. However, there is at least one other significant ferric complex in seawater above p[H⁺] = 8.0 (possibly with bicarbonate, carbonate, or borate ions) in addition to the Fe(OH)₂⁺ and Fe(OH)₃⁰ species.     

Effect of major ion variations in the marine environment on the specific gravity-conductivity-chlorinity-salinity relationship

Partial equivalent conductances and partial equivalent volumes of the major constituents in seawater were used to evaluate the specific gravity-conductivity-chlorinity-salinity relationships in the marine environment. For example, in the open ocean, the relationships between Cl‰ and both S‰ and specific gravity are valid to within 0.014‰ and 0.014 σ_t, respectively. The relationships between conductivity and S‰ and specific gravity are valid to within 0.006‰ and 0.007 σ_t. In river diluted nearshore areas specific gravity anomalies inferred from Cl‰, can be as great as 0.06 σ_t and 0.04 σ_t when inferred from a conductivity ratio measurement.     

The distribution of total and electrochemically available copper in the northwestern atlantic ocean

Copper in a series of samples from the northwestern Atlantic has been determined by anodic stripping voltammetry (ASV) and atomic absorption spectrometry after preconcentration by cobalt—APDC coprecipitation. Samples from a transect across the continental shelf directly off the New York Bight showed a linear relationship between total copper and salinity (31–34‰) and less than 5% of the total copper was detectable by ASV. A slope water station showed less than 9% of the total copper to be ASV detectable in the upper 780m, below which the ASV detectable copper increased to 70% at 3000 m. The Sargasso Sea profiles showed less than 7% ASV detectable copper in the upper 150 m; the fraction of the total copper detected by ASV increased to about 80% of the total copper at greater depths. The reduced availability of copper to the ASV measurement in coastal waters and open ocean surface waters appears to be related to recent contact with waters where biological productivity occurs.     

The MV Rena shipwreck: time-critical scientific response and environmental legacies

ABSTRACT

The sinking of the MV Rena on Astrolabe Reef (Otaiti) in the Bay of Plenty, New Zealand, resulted in the release of oil and ship debris, including dangerous goods carried as cargo. Two key questions of concern to the public and environmental managers were posed immediately: what was the impact of the Rena oil spill and how long would it take for the marine environment to recover? The research that began immediately after the ship grounded provided answers, as documented in this special issue.     

THE HYDROGEOLOGY OF GHANA

SUMMARY

Many hydrological systems exhibit long periods of quiescent behaviour, broken only occasionally by short periods of comparatively intense activity. Clear examples arise in stream run-off measurements and in ground water table observations. The number of measurements recorded can then be considerably reduced by reducing the frequency of recording over the quiescent periods. The paper describes an algorithm whereby this reduction is attained in an optimum manner. When recordings can be accepted directly by a computer, the algorithm simply provides a translation programme Whereby the quality of data may be very considerably reduced. Other applications are, however, discussed.

The problems of Optimum representations is first presented, and choices of norm indicated. Using a particular norm, it is shown that the optimum representation is characterised, under certain limiting conditions, by the property that the second moments of the second derivatives are constant over all optimum intervals. This characterisation is used to construct an iterative difference scheme, whereby a certain truncation error is accepted. Sufficient conditions for stability of the scheme are determined and these incorporated into a computer programme. The programme has been tested on a variety of data with satisfactory results. In conclusion, a further development of the method is indicated.     

Thermodynamic stability studies of the basic copper carbonate mineral,malachite

Natural malachite is a well defined solid demonstrating reproducible solubility behavior over a wide range of pH. The following equilibrium constants associated with the malachite dissolution equilibrium at 25°C, 1 atm were determined:

(infinite dilution)

$\text{K}{}^1{}_{\mathrm{sp}}\text{=}\text{[Cu}{}^{\mathrm{2+}}\text{]}{}^2\text{[CO}{}^{\mathrm{2?}}{}_3\text{]K}{}^2{}_{\mathrm{w}}\text{a}{}^2{}_{\mathrm{H+}}\text{= 10. ± 0.2 × 10}{}^{\mathrm{?32}}$

(0.72 ionic strength)

(36.9‰ salinity seawater). The temperature dependence of a “mixed” equilibrium constant, K_sp⁺, of the form:

has been measured at I = 0.72, yielding the relationship:

$\text{log K}{}^2{}_{\mathrm{sp}}\text{= (? 9.8 ± 0.03) × 10}{}^4\text{(}\text{1}\text{T°K}\text{) + (1.52 ± 0.09)}$

within a 5–25°C temperature range. The effect of pressure on the solubility of malachite in water and seawater was estimated from partial molar volume and compressibility data. For 25 °C at infinite dilution $\text{K'}{}_{\mathrm{sp}}\text{(1000 bar)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 240}$ and in seawater $\text{K′}{}_{\mathrm{sp}}\text{(1000)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 44}$.Comparison of stoichiometric and apparent malachite equilibrium constants has been used to estimate the extent of copper(II) ion interaction at the ionic strength of seawater. In dilute carbonate medium (total alkalinity, TA = 2.4 meq/kg H₂O, pH 8.3), 2.9% of total dissolved copper exists as the free copper(II) ion and in seawater (S = 36.9%., TA = 2.3 meq/kg H₂O, pH = 8.1), $\text{[Cu}{}^{\mathrm{2+}}\text{]}\text{T(Cu)}$ is 3.1%.Total dissolved copper levels of approximately 450–750 nMol/Kg are necessary to attain malachite saturation conditions in the open ocean. Observations of malachite particles suspended in seawater must be explained by precipitation or solid phase substitution reactions from localized environments rather than by direct precipitation from bulk seawater.     

Magnetospheric accretion and pre-main-sequence stellar masses

We present a method of determining lower limits on the masses of pre-main-sequence (PMS) stars and so constraining the PMS evolutionary tracks. This method uses the redshifted absorption feature observed in some emission-line profiles of T Tauri stars, indicative of infall. The maximum velocity of the accreting material measures the potential energy at the stellar surface, which, combined with an observational determination of the stellar radius, yields the stellar mass. This estimate is a lower limit owing to uncertainties in the geometry and projection effects. Using available data, we show that the computed lower limits can be larger than the masses derived from PMS evolutionary tracks for M   0.5 M. Our analysis also supports the notion that accretion streams do not impact near the stellar poles but probably hit the stellar surface at moderate latitudes.     

Ultraviolet spectroscopic determination of the stability constants for copper carbonate and bicarbonate complexes up to the ionic strength of seawater

An ultraviolet spectroscopic study at 25°C is used to determine the stoichiometric stability constant of CuCO₃⁰ (β_CuCO3⁰) over a range of ionic strengths; extrapolation to zero ionic strength provides a thermodynamic constant (log β⁰_CuCO3⁰ = 6.89). At 0.69 m ionic strength, log β_CuCO3⁰) is 6.33.This study provides the first experimental evidence for the existence of CuHCO₃⁺. At 0.69 m ionic strength, log β_CuHCO3⁺ is 2.77.The ultraviolet molal absorptivity spectra for the two complexes are also determined. The spectrum for CuCO₃⁰ consists of a single band centered at 276.5 nm and was described well by a Gaussian function. The spectrum of CuHCO₃⁺ consists of at least two overlapping bands.Side reactions which might affect the data interpretation were included in the analysis of the results. The effects of the Cu(II) hydrolysis reactions were accounted for by using data from previous work, and possible effects due to copper-organic species were eliminated by a subtraction procedure.