Determination of picomolar iron in seawater by double Mg(OH)2 precipitation isotope dilution high-resolution ICPMS

A low-blank pre-concentration procedure is described for the analysis of picomolar iron (Fe) in seawater by isotope dilution high-resolution inductively coupled plasma mass-spectrometry (HR-ICPMS). The procedure uses a two-step Mg(OH)₂ co-precipitation procedure to extract Fe from a 50 ml seawater sample into a 100 μl 4% nitric acid (HNO₃) solution followed by HR-ICPMS measurement. The high pre-concentration ratio ( 500:1) achieved by the procedure minimizes the Fe blank due to ICPMS instrumental Fe background and results in a detection limit of  2 pM and a precision of  4% at the 50 pM Fe level. The measurement of a low-Fe seawater sample spiked with gravimetric Fe standard shows that the method can clearly distinguish 0.01 nM Fe from 0.02 nM Fe in seawater with high accuracy. The method is demonstrated by the analysis of dissolved Fe in the equatorial Pacific Ocean.     

Determination of the complexing capacity and conditional stability constants of complexes of copper(II) with natural organic ligands in seawater by cathodic stripping voltammetry of copper-catechol complex ions

A new method is proposed for the determination of complexing capacities and conditional stability constants for complexes of copper(II) with dissolved organic ligands in seawater. This method is based on ligand competition by the added ligand catechol for free metal ions. The concentration of copper-catechol complex ions is measured with great sensitivity by cathodic stripping voltammetry. The concentration of the free copper ion is calculated from the concentration of copper-catechol complex ions. Ligand concentrations and conditional stability constants are obtained from a titration of the ligands with copper. Two techniques for treatment of the data are compared. A seawater sample, originating from open oceanic conditions, is analysed and two complexing ligands were detected, having concentrations of 1.1 × 10^?8 and 3.3 × 10^?8 M, and conditional stability constants (log K′_CuL) of 12.2 and 10.2, respectively.     

The interaction of manganese(II) with the surface of calcite in dilute solutions and seawater

The interaction of Mn²⁺ with the surface of calcite in aqueous solutions is complex. In dilute solutions the Mn²⁺ is rapidly absorbed, MnCO3₃ nucleates on the calcite surface and then grows by a first order reaction with respect to the initial Mn²⁺ concentration. At higher ionic strengths in NaCl solutions, the rate of these processes is slower, but the same general pattern persists. In solutions containing Mg²⁺, at the concentration of seawater and in seawater, the nucleation phase of the uptake process does not appear to occur. The long-term uptake rate of Mn²⁺ on the surface of calcite in seawater is first order with respect to the dissolved Mn²⁺ concentration. The rate constant is over three orders of magnitude smaller than that found in dilute Mg²⁺-free solutions. A probable explanation for the slower growth rate in seawater is that MnCO₃ is not nucleated on the calcite surface due to the presence of high Mg²⁺ concentrations. The Mg²⁺, through site competition, prevents enough Mn²⁺ from being adsorbed to reach a critical concentration for MnCO₃ nucleation. This behavior is similar to that found for orthophosphate with calcite surfaces in dilute solutions and seawater. It indicates that rhodochrosite cannot nucleate in carbonate-rich recent sediments unless the Mg²⁺ concentration is lowered below that of seawater.Measurements of the solubility of rhodochrosite in seawater gave results from an undersaturation approach to equilibrium in excellent agreement with those found in previous studies in dilute solutions. When equilibrium was approached from supersaturation, approximately fifty times more calcium was precipitated than Mn²⁺. The measured solubility was over twice that determined from undersaturation. It is possible that a Mn—calcite containing 25 to 30 mol% MnCO₃ formed on the rhodochrosite from the supersaturated solutions. Consequently, it is doubtful that pure rhodochrosite controls the concentration of Mn²⁺ even in calcium carbonate-poor marine environments.     

Interactions of cadmium(II) and protons with dead biomass of marine algae Fucus sp.

Samples of dead biomass from the marine brown algae Fucus ceranoides, Fucus vesiculosus and Fucus serratus were studied for their ability to remove cadmium from aqueous solutions. The metal sorption process is rapid, with 90% of the metal uptake completed within the first 25 min of contact. The kinetic data was described successfully by a pseudo second order chemical sorption process with rate constants of ca. 0.6 g mmol^− 1 min^− 1. At pH 4.5, the raw biomass of the three species exhibited equilibrium uptake capacities for Cd as high as 0.8 mmol g^− 1 (90 mg g^− 1), on a dry weight basis, without chemical pretreatment. These sorption capacities are much higher than those reported for activated carbon and chitin. The sorption of Cd was found to increase as pH increases, reaching a plateau at pH 5.Batch sorption experiments and continuous potentiometric titrations of acid-treated biomass samples in 0.05 M NaNO₃ were used to derive thermodynamic binding parameters according to the NICCA model. The total amount of acid sites was 2.4–2.9 mmol g^− 1, with median values of the affinity distribution for protons and cadmium ions, log K˜_H and log K˜_Cd, of 3.7 and 2.69, respectively (conditional values). The apparent heterogeneity of the sorbent was successfully taken into account by the empirical NICCA isotherm, which described very well the competition between protons and metal ions, in contrast with a simpler discrete competitive Langmuir model.The experimental results demonstrate that these seaweeds constitute a promising, efficient, cheap and biodegradable sorbent biomaterial for cadmium removal from wastewaters. This use would represent an example of exploitation of a renewable marine resource in water treatment technologies for the prevention of heavy metal pollution in the environment.     

海水中超低含量活性磷酸盐的Mg(OH)2共沉淀法测定研究

活性磷(正磷酸盐)是海洋浮游植物生长所必需的物质基础[1-8],磷的生物可利用性直接影响全球的初级生产力水平.磷在特定的海洋环境中还可能限制固氮作用,成为限制海洋初级生产力的重要因素[1,3,6].海水中磷酸盐含量的测定也是海洋污染调查的重要指标之一[4,9].农业和工业废水中磷的过度排放导致河口和近岸海水富营养化,引起浮游植物异常繁殖,造成“赤潮”现象[4].因此,海水中磷的准确测定对深入理解生物地球化学过程及海洋环境保护具有重要理论和实际意义[4-6,9].磷钼蓝分光光度法是海水中活性磷的经典测定方法,检测限为324 nmo1/dm3[5],但在一些寡营养盐海域,例如在南海、地中海     

Comparison of the effects of water-soluble (EDTA) and particulate (Chelex-100) synthetic ligands on the growth of phytoplankton population in the disphotic zone seawater

To clarify the beneficial roles of naturally occurring organic ligands on the growth of phytoplankton in newly upwelled water, phytoplankton culture experiments using disphotic zone water were conducted to discriminate between the effects of EDTA in the detoxification of certain toxic metal ions and increasing the availability of essential metals. Culture media were prepared by adding EDTA and Chelex-100, separately or in combination, to disphotic zone water samples. Our proposed working hypothesis is that phytoplankton growth can be enhanced by removing toxic metal ions from culture media by Chelex-100 and by detoxification of toxic metal ions or increasing the availability of essential metals by EDTA. A shortening of the lag period and an increase of the specific population growth rate were clearly observed after the addition of Chelex-100; nd EDTA. The effects of EDTA were more considerable than those of Chelex-100; a 17 to 44% in shortening the lag period and a 35 to 56% increase in the growth rate, when comparing the effects of Chelex-100 with those of EDTA. The similar effects of removing toxic metal ion by Chelex-100 as those of detoxification by EDTA suggested that EDTA has a role not only of detoxification but also of increasing the availability of essential metals. The present study suggests that the low productivity in newly upwelled water observed by Barber and Ryther (1969) can be ascribed to both toxic metal ions and a lack of available forms of essential metals because of their low contents of free natural organic ligands.     

Short-term variability of fCO2 in seawater and air–sea CO2 fluxes in a coastal upwelling system (Ría de Vigo, NW Spain)

Coastal upwelling systems are regions with highly variable physical processes and very high rates of primary production and very little is known about the effect of these factors on the short-term variations of CO₂ fugacity in seawater (fCO₂^w). This paper presents the effect of short-term variability (<1 week) of upwelling–downwelling events on CO₂ fugacity in seawater (fCO₂^w), oxygen, temperature and salinity fields in the Ría de Vigo (a coastal upwelling ecosystem). The magnitude of fCO₂^w values is physically and biologically modulated and ranges from 285 μatm in July to 615 μatm in October. There is a sharp gradient in fCO₂^w between the inner and the outer zone of the Ría during almost all the sampling dates, with a landward increase in fCO₂^w.CO₂ fluxes calculated from local wind speed and air–sea fCO₂ differences indicate that the inner zone is a sink for atmospheric CO₂ in December only (−0.30 mmol m⁻² day⁻¹). The middle zone absorbs CO₂ in December and July (−0.05 and −0.27 mmol·m⁻² day⁻¹, respectively). The oceanic zone only emits CO₂ in October (0.36 mmol·m⁻² day⁻¹) and absorbs at the highest rate in December (−1.53 mmol·m⁻² day⁻¹).