Oceanic Behavior

In oxygenated seawater, uranium is thermodynamically predicted to be present in a hexavalent (-b 6) oxidation state, but it can also exist as the tetravalent U(IV) if conditions are sufficiently reducing. Reduced uranium in the +A oxidation state is highly insoluble or particle reactive. In contrast, U(VI) is readily soluble due to the rapid formation of stable inorganic carbonate complexes. According 

Donat and K. W. Bruland, in Trace Elements in the Oceans, ed. B. Salbu and E. Steinnes, CRC Press, Boea Raton, EL, 1995, pp. 247-281. 

Owing to the stability of the uranyl carbonate complex, uranium is universally present in seawater at an average concentration of ca. 3.2/rgL with a daughter/parent activity ratio U) of 1.14. In particulate matter and bottom sediments that are roughly 1 x 10 years old, the ratio should approach unity (secular equilibrium). The principal source of dissolved uranium to the ocean is from physicochemical weathering on the continents and subsequent transport by rivers. Potentially significant oceanic U sinks include anoxic basins, organic rich sediments, phosphorites and oceanic basalts, metalliferous sediments, carbonate sediments, and saltwater marshes.  

Removal of uranium from solution can take place by various mechanisms. Calcareous and siliceous organisms can efficiently remove uranium from 

Church, M. M. Sarin, M. Q. Eleisher and T. G. Eerdelman, Geochim. Cosmochim. Acta, 1996, 

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Redox-controlled type Elements such as Cr, As, Se, and Te exist in sea water at more than one oxidation state. Their oceanic behavior is strongly dependent on the chemical form. Their reduced states are thermodynamically unstable in normal oxygenated waters but are probably formed through biological mediation. Reduced species can also be formed in anoxic basins, the Black Sea, Cariaco Trench, some fiords, and in organic-rich sediments. 

Conservative type Some of the trace elements such as U, W, and Re form stable ionic species, UOiiCOs) , WOl , and ReOj in sea water. Hence, their oceanic behavior is conservative (follow salinity) and their mean residence times in the ocean are generally long (e.g., >10 years). There is no significant variation in their concentration between different oceanic basins. 

For a radionuclide to be an effective oceanic tracer, various criteria that link the tracer to a specihc process or element must be met. Foremost, the environmental behavior of the tracer must closely match that of the target constituent. Particle affinity, or the scavenging capability of a radionuclide to an organic or inorganic surface site i.e. distribution coefficient, Kf, is one such vital characteristic. The half-life of a tracer is another characteristic that must also coincide well with the timescale of interest. This section provides a brief review of the role of various surface sites in relation to chemical scavenging and tracer applications. 

The majority of published °Pb reports address the utility of °Pb as a geochronological tool rather than as an element that is involved in complex biogeochemical cycles. Nonetheless, some of these studies do provide insight into the geochemical behavior of °Pb and °Po. Nearly all of the lead in the world s surface oceans is believed to be of anthropogenic origin—derived from combustion... 

Observations of the ratio of oxidized plutonium to reduced plutonium may provide some insight to the observations of erratic formation and lack of equilibration in laboratory solutions at ORNL versus fairly consistent and predictable behavior in oligo-trophic lakes and marine systems. In coastal water and the relatively shallow Lake Michigan, Pu(V) is about 90 percent of the soluble plutonium, but in the upper waters of the open ocean, where it does not interact with the seafloor due to the depths,... 

Why are the oceans so depleted in these trace metals Certainly it is not for the lack of availability from rock weathering or because of constraints imposed by the solubility of any unique compound of these elements. The reason must lie in the dynamics of the system of delivery of the metals to the oceans and their subsequent behavior in an ocean that cannot be simulated by simple in vitro experiments involving homogeneous reaction kinetics. 

Referring to the discussion of the fundamental concepts regarding half cells and the Nernst equation in Chapter 5 (Section 5.3.1) it is possible to briefly summarize the similarities and differences of these two sets of systems. It is important to recognize the ways in which they are different when considering the behavior of complex multivariate systems such as the oceans and clouds, or a lake-river system. 

Chapters 11 and 12 focus on the oceans. The first of these describes the use of U-series nuclides in the modern ocean, where they have been particularly useful during the last decade to study the downward flux of carbon. The second ocean chapter looks at the paleoceanographic uses of U-series nuclides, which include assessment of sedimentation rates, ocean circulation rates, and paleoproductivity. Both of these ocean chapters demonstrate that knowledge of the behavior of the U-series is now sufficiently well developed that their measurement provides useful quantitative information about much more than just the geochemistry of these elements. 

This chapter summarizes the use of U-series nuclides in paleoceanography. It starts with a brief summary of the oceanic U budget and an introduction to important features of the behavior of U-series nuclides in the marine realm. It then discusses the various U-series tools which have proved useful for paleoceanography, starting at U (and U) and progressing down the decay chain towards Pb. One tool that will not be discussed is U/Th dating of marine carbonates which has seen sufficient application to merit a chapter on its own (Edwards et al. 2003). The use of U-series nuclides to assess rates of processes in the modem ocean will also not be discussed in depth here but are dealt with elsewhere in this volume (Cochran and Masque 2003). 

The chemical behavior of U and its daughter nuclides in the ocean environment was extensively studied in the 1960s and 1970s and has been well summarized (Cochran 1992). The most important mechanism by which nuclides are separated from one another to create disequilibrium is their differing solubility. For U, this solubility is in turn influenced by the redox state. The process of alpha-recoil can also play an important role in producing disequilibrium. 

Thorium generally exists as a neutral hydroxide species in the oceans and is highly insoluble. Its behavior is dominated by a tendency to become incorporated in colloids and/or adhere to the surfaces of existing particles (Cochran 1992). Because ocean particles settle from the water column on the timescale of years, Th isotopes are removed rapidly and have an average residence time of = 20 years (Fig. 1). This insoluble behavior has led to the common assertion that Th is always immobile in aqueous conditions. While this is generally true in seawater, there are examples of Th being complexed as a carbonate (e.g.. Mono Lake waters, Anderson et al. 1982 Simpson et al. 1982) in which form it is soluble. 

Figure 8. Partition coefficients (Kd) for Th and Pa and the fractionation factor (F) between Th and Pa plotted as a function of the opal and calcium carbonate percentage in settling particulate material. Note the tendency for the Kd for Th to increase with increasing carbonate fraction and decrease with increasing opal fraction. Pa shows the opposite behavior so that F increases with low opal fraction or high carbonate fraction. This plot is modified from Chase et al. (in press-b) but excludes the continental margin data also shown in that study and instead focuses exclusively on open-ocean sites.

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