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The oxidation of nanomolar copper(I) at low oxygen (6 μM) concentrations was studied as a function of pH (6.7-8.2), ionic strength (0.1-0.76 M), total inorganic carbon concentration (0.65-6.69 mM), and the added concentration of hydrogen peroxide, H(2)O(2) (100-500 nM) over the initial 150 nM H(2)O(2) concentration in the coastal seawater. The competitive effect between H(2)O(2) and O(2) at low O(2) concentrations has been described. Both the oxidation of Cu(I) by oxygen and by H(2)O(2) had a reaction order of one. The reduction of Cu(II) back to Cu(I) in the studied seawater by H(2)O(2) and other reactive oxygen intermediates took place at both high and low O(2) concentrations. The effect of the pH on oxidation was more important at low oxygen concentrations, where δlog k/δpH was 0.85, related to the presence of H(2)O(2) in the initial seawater and its role in the redox chemistry of Cu species, than at oxygen saturation, where the value was 0.6. A kinetic model that considered the Cu speciation, major ion interactions, and the rate constants for the oxidation and reduction of Cu(I) and Cu(II) species, respectively, was applied. When the oxygen concentration was lower than 22 μM and under the presence of 150 nM H(2)O(2), the model showed that the oxidation of Cu(I) was controlled by its reaction with H(2)O(2). The effect of the pH on the oxidation rate of Cu(I) was explained by its influence on the oxidation of Cu(I) with O(2) and H(2)O(2), making the model valid for any low oxygen environment.

The Fe(II) oxidation kinetic was studied in seawater enriched with nutrients as a function of pH (7.2-8.2), temperature (5-35 °C), and salinity (10-36.72) and compared with the same parameters in seawater media. The effect of nitrate (0-1.77 × 10(-3) M), phosphate (0-5.80 × 10(-5) M) and silicate (0-2.84 × 10(-4) M) was studied at pH 8.0 and 25 °C. The experimental results demonstrated that Fe(II) oxidation was faster in high nutrient concentrations affecting the lifetime of Fe(II) in nutrient rich waters. Silicate displayed the most significant effects on the Fe(II) oxidation rate with values similar to those determined in seawater enriched with all the nutrients. A kinetic model was applied to the experimental results in order to account for changes in the speciation and to compute the fractional contribution of each Fe(II) species to the total rate constant as a function of pH. FeH(3)SiO(4)(+) played a key role in the Fe(II) speciation, dominating the process at pH over 8.4. At pH 8.0, FeH(3)SiO(4)(+) represented 18% of the total Fe(II) species. Model results show that when the concentration of silicate is 3 × 10(-5) M as in high nutrient low chlorophyll areas, FeH(3)SiO(4)(+) contributed at pH 8.0 by 4% increasing the rate to 11% at 1.4 × 10(-4) M. The effect of nutrients, especially silicate, must be considered in any further study in seawater media cultures and eutrophic oceanic areas.

The oceans are a major sink for atmospheric carbon dioxide (CO2). Historically, observations have been too sparse to allow accurate tracking of changes in rates of CO2 uptake over ocean basins, so little is known about how these vary. Here, we show observations indicating substantial variability in the CO2 uptake by the North Atlantic on time scales of a few years. Further, we use measurements from a coordinated network of instrumented commercial ships to define the annual flux into the North Atlantic, for the year 2005, to a precision of about 10%. This approach offers the prospect of accurately monitoring the changing ocean CO2 sink for those ocean basins that are well covered by shipping routes.

The oxidation of Fe(II) by molecular oxygen at nanomolar levels has been studied using a UV-Vis spectrophotometric system equipped with a long liquid waveguide capillary flow cell. The effect of pH (6.5-8.2), NaHCO3 (0.1-9 mM), temperature (3-35 degrees C), and salinity (0-36) on the oxidation of Fe(II) are presented. The first-order oxidation rates at nanomolar Fe(II) are higher than the values at micromolar levels at a pH below 7.5 and lower than the values at a higher pH. A kinetic model has been developed to consider the mechanism of the Fe(II) oxidation and the speciation of Fe(II) in seawater, the interactions between the major ions, and the oxidation rates of the different Fe(II) species. The concentration of Fe(II) is largely controlled by oxidation with O2 and O2.- but is also affected by hydrogen peroxide that may be both initially present and formed from the oxidation of Fe(II) by superoxide. The model has been applied to describe the effect of pH, concentration of NaHCO3, temperature, and salinity on the kinetics of Fe(II) oxidation. At a pH over 7.2, Fe(OH)2 is the most important contributing species to the apparent oxidation rate. At high levels of CO3(2-) and pH, the Fe(CO3)2(2-) species become important. At pH values below 7, the oxidation rate is controlled by Fe2+. Using the model, log k(i) values for the most kinetically active species (Fe2+, Fe(OH)+, Fe(OH)2, Fe(CO3), and Fe(CO3)2(2-)) are given that are valid over a wide range of temperature, salinity, and pH in natural waters. Model results showthatwhen H2O2 concentrations approach the Fe(II) concentrations used in this study, the oxidation of Fe(II) with H2O2 also needs to be considered.