Seawater silicate

The zinc silicate, epoxy and coal tar/epoxy coatings are still used. Coal tar epoxies are used for crude oil tanks, sometimes on all the interior surfaces but more often for a) the bottom of the tank and about 2 m up the sides, b) the top of the tank and about 2 m down the sides, and (c) other horizontal surfaces where seawater ballast may lie. These partly coated tanks are frequently also fitted with cathodic protection to prevent corrosion of the uncoated areas when seawater ballast is carried. The pure epoxy or coal tar epoxy coatings applied in bulk cargo tanks used for the carriage of grain must be approved by the North of England Industrial Health Service, or by similar independent authorities in other countries. 

Silicic acid (H4Si04) is a necessary nutrient for diatoms, who build their shells from opal (Si02 H20). Whether silicic acid becomes limiting for diatoms in seawater depends on the availability of Si relative to N and P. Estimates of diatom uptake of Si relative to P range from 16 1 to 23 1. Dugdale and Wilkerson (1998) and Dunne et al. (1999) have shown that much of the variability in new production in the equatorial Pacific may be tied to variability in diatom production. Diatom control is most important at times of very high nutrient concentrations and during non-steady-state times, perhaps because more iron is available at those times. 

The failure to identify the necessary authigenic silicate phases in sufficient quantities in marine sediments has led oceanographers to consider different approaches. The current models for seawater composition emphasize the dominant role played by the balance between the various inputs and outputs from the ocean. Mass balance calculations have become more important than solubility relationships in explaining oceanic chemistry. The difference between the equilibrium and mass balance points of view is not just a matter of mathematical and chemical formalism. In the equilibrium case, one would expect a very constant composition of the ocean and its sediments over geological time. In the other case, historical variations in the rates of input and removal should be reflected by changes in ocean composition and may be preserved in the sedimentary record. Models that emphasize the role of kinetic and material balance considerations are called kinetic models of seawater. This reasoning was pulled together by Broecker (1971) in a paper called "A kinetic model for the chemical composition of sea water."... 

Various approaches to the analysis of dissolved silicon have been tried. Most of them are based on the formation of /J-molybdosilic acid [ 199-203 ]. Dissolved silicon exists in seawater almost entirely as undissociated orthosilicic acid. This form and its dimer, termed reactive silicate , combine with molybdosilicic acid to form a- and /I-molybdosilicic acid [180]. The molybdosilicic acid can be reduced to molybdenum blue, which is determined photometrically [206]. The photometric determination of silicate as molybdenum blue is sufficiently sensitive for most seawater samples. It is amenable to automated analysis by segmented continuous flow analysers [206-208]. Most recent analyses of silicate in seawater have, therefore, used this chemistry. Furthermore, reactive silicate is probably the only silicon species in seawater that can be used by siliceous organisms [204]. 

Spencer and Brewer [111] have reviewed methods for the determination of silicate in seawater. Various workers [209-212] have studied the application of molybdosilicate spectrophotometric methods to the determination of silicate in seawater. In general, these methods give anomalous results due, it is believed, to erratic blanks and uncertainty regarding the structure of the silicomolybdate formed. 

Brzelinski and Nelson [214] have described a solvent extraction procedure for the spectrophotometric determination of nanomolar concentrations of silicic acid in seawater. 

Flow injection analysis is a rapid method of automated chemical analysis that allows for quasi-continuous recording of nutrient concentrations in a flowing stream of seawater. The apparatus used for flow injection analysis is generally less expensive and more rugged than that used in segmented continuous flow analysis. A modified flow injection analysis procedure, called reverse flow injection analysis, was adopted by Thompson et al. [213] and has been adapted for the analysis of dissolved silicate in seawater. The reagent is injected into the sample stream in reverse flow injection analysis, rather than vice versa as in flow injection analysis. This results in an increase in sensitivity. 

Brewer and Spencer [428] have described a method for the determination of manganese in anoxic seawaters based on the formulation of a chromophor with formaldoxine to produce a complex with an adsorption maximum at 450 nm. Sulfide (50 xg/l), iron, phosphate (8 ig/l), and silicate (100pg/l) do not interfere in this procedure. The detection limit is 10 pg/1 manganese. 

The latter two assumptions are simplistic, considering the number of factors that affect pH and oxidation state in the oceans (e.g., Sillen, 1967 Holland, 1978 McDuff and Morel, 1980). Consumption and production of CO2 and O2 by plant and animal life, reactions among silicate minerals, dissolution and precipitation of carbonate minerals, solute fluxes from rivers, and reaction between convecting seawater and oceanic crust all affect these variables. Nonetheless, it will be interesting to compare the results of this simple calculation to observation. 

When magnesium sulphate was omitted from distilled water samples of phosphorus compounds, recovery was variable. Table 12.11 shows yields of a series of standards with and without the magnesium sulphate addition and with and without the final hydrolysis. The magnesium sulphate is used as an acidic solution (after addition to the seawater sample, the pH was about 3) to minimize silicate leaching from the glassware during evaporation. The acid and heating are necessary to hydrolyse any condensed phosphates in the final mixture. 

Sediment reference materials should be developed for both open-ocean and coastal areas. Open-ocean sediments should include carbonate-rich, silicate-rich, and clay mineral-rich types. Coastal sediments should be of the same types and should include a deltaic sediment that has not been in contact with seawater. Taken together with the algal-based materials, these sediment materials would represent a wide range of diagenetic states. The committee recommends that each of these solid... 

Matrix effects in the analysis of nutrients in seawater are caused by differences in background electrolyte composition and concentration (salinity) between the standard solutions and samples. This effect causes several methodological difficulties. First, the effect of ionic strength on the kinetics of colorimetric reactions results in color intensity changes with matrix composition and electrolyte concentration. In practice, analytical sensitivity depends upon the actual sample matrix. This effect is most serious in silicate analysis using the molybdenum blue method. Second, matrix differences can also cause refractive index interference in automated continuous flow analysis, the most popular technique for routine nutrient measurement. To deal with these matrix effects, seawater of... 

Reference materials that represent the primary deep-sea and coastal depositional environments and biological materials would solve many of the problems that radiochemists face in analysis of sediments from these settings. Radiochemists require reference materials comprising the primary end member sediment and biological types (calcium carbonate, opal, and red clay from the deep-sea and carbonate-rich, silicate-rich, and clay mineral-rich sediments from coastal environments and representative biological materials). Additional sediment reference material from a river delta would be valuable to test the release of radionuclides that occurs as riverine particles contact seawater. 

Speciation calculations can be performed for the weak acids and bases in a feshion similar to that presented earlier for Fe(III). The results of these calculations as a function of pH are shown in Figure 5.19. At the pH of seawater, the dominant species are carbonate, bicarbonate, ammonium, hydrogen phosphate, dihydrogen phosphate, and boric and silicic acid. In waters with low O2 concentrations, significant concentrations of HS can be present. 

Sampling sites are also referred to as station locations. For water column work, depth profiles are constructed from seawater samples collected at representative depths. Temperature and salinity are measured in situ with sensors. Remote-closing sampling bottles deployed from a hydrowire are used to collect water for later chemical analysis, either on the ship or in a land-based laboratory. The standard chemical measurements made on the water samples include nutrients (nitrate, phosphate, and silicate), dissolved O2, and total dissolved inorganic carbon (TDIC) concentrations. 

Silicon undergoes internal cycling within the crustal-ocean-atmosphere fectory dm-ing which mineral silicates are produced via precipitation from seawater. These include biotic and abiotic precipitates. As compared to the crystalline silicates that ultimately originate from the igneous rocks, the precipitates are amorphous in structme. To distinguish them from the crystalline silicates, the amorphous forms are collectively referred to as opaline silica. 

Finally, some authigenic clay minerals are produced by the reaction of seawater with fresh volcanic glass. This commonly occurs near mid-ocean ridges and rises or where lava from coastal volcanoes flows into the sea. Clay minerals produced by this process are primarily smectites, such as montmorillonite, and a type of framework silicate called zeolites of which phillipsite and clinoptilite are the most common marine examples. Zeolites are characterized by three-dimensional frameworks with large cavities that... 

Changes in phosphate, nitrate, ammonia, and silicate concentrations associated with the biogenic production and destruction of POM can alter seawater alkalinities. These effects are usually so small in scale that they can be ignored. Since the largest biotic impact on alkalinity in oxic seawater is exerted by the formation and dissolution of... 

At the pH and ionic strength of seawater, the dominant dissolved species of silicon is orthosilicic acid [H4Si04(aq) or Si(OH)4(aq)]. The speciation of silicic acid is shown in Figure 5.19. At the pH of seawater, a minor amount of dissociation occurs, such that about 5% of the dissolved silicon is in the form of HjSiO faq). Dissolved organic complexes of silicon do not occur naturally. 

Since all seawater is undersaturated with respect to BSi, plankton that deposit siliceous hard parts must fight unfevorable thermodynamics. In the case of the diatoms, the phytoplankton have specialized proteins that help concentrate the DSi intracellularly... 

In contrast to calcium carbonate, all seawater is undersaturated with respect to BSi. As shown in Table 16.1, the imdersaturation is very large and increases with depth because the solubility of BSi increases with pressure. Thus, all siliceous hard parts are subject to dissolution. Nevertheless, about 25% of the BSi created in the surfece waters survives the trip to the seafloor via pelagic sedimentation. Direct observations of this transport... 

As with the calcareous tests, BSi dissolution rates depend on (1) the susceptibility of a particular shell type to dissolution and (2) the degree to which a water mass is undersaturated with respect to opaline silica. Susceptibility to dissolution is related to chemical and physical factors. For example, various trace metals lower the solubility of BSi. (See Table 11.6 for the trace metal composition of siliceous shells.) From the physical perspective, denser shells sink fester. They also tend to have thicker walls and lower surface-area-to-volume ratios, all of which contribute to slower dissolution rates. As with calcivun carbonate, the degree of saturation of seawater with respect to BSi decreases with depth. The greater the thermodynamic driving force for dissolution, the fester the dissolution rate. As shown in Table 16.1, vertical and horizontal segregation of DSi does not significantly coimter the effect of pressure in increasing the saturation concentration DSi. Thus, unlike calcite, there is no deep water that is more thermodynamically favorable for BSi preservation they are all corrosive to BSi. 

Reaction with heated seawater transforms the peridotite into a hydrous Mg-silicate mineral called serpentine. Hence, this process is called serpentinization, as illustrated for a common mineral in peridotite, olivine ... 

The model provided in Figure 20.1 is for an ocean basin whose abyssal plains all lie below the CCD. This most closely resembles the conditions in the North Pacific, whereas the rest of the ocean basins have a significant portion of their abyssal plains lying above the CCD, and, hence, contain some calcareous oozes. From a global perspective, calcareous oozes are more abundant than siliceous oozes. This is caused by two phenomena (1) all seawater is undersaturated with respect to opal, whereas all surface waters and 20% of the deep waters are saturated with respect to calcite, and (2) siliceous plankton are dominant only in upwelling areas. 

For example, organic matter deeply embedded in the mineral matrix of biogenous hard parts would not be exposed to exoenzyme attack. This embedding could occur during deposition of the minerals or through adsorption of the organic matter from seawater. Most of the ballasting effect exerted on POM is conferred by calcareous and siliceous hard parts and by clay minerals. 

Annual mean surface seawater concentrations of (a) chlorophyll (b) nitrate, (c) phosphate, (d) silicate, and (e) iron. Data from Conkright, M., et al. (2002). World Ocean Atlas 2001 Vol. 4 Nutrients. Vol. NOAA Atlas NESDIS 52. U.S. Government Printing Office. Plots from M. Vichi, et al. (2007). Journal of Marine Systems 64, 110-134. (See companion website for color version.)... 

The above-listed factors concur simultaneously to define the stationary chemistry of seawater. Moreover, the control operated by the various phenomena is selective for the various types of elements for instance, the amounts of Ca are largely controlled by precipitation of carbonates, those of Na and K by silicate hydroly-... 

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