Seawater buffer

Finally, the inorganic carbon equilibrium is responsible for buffering seawater at a pH near 8 on timescales of centuries to millennia. 

Although less energetically efficient than the oxidation of hydrogen sulphide (Fig. 8.4), the oxidation of metal sulphides could potentially support chemo-synthesis at seafloor massive sulphide deposits long after hydrothermal activity had ceased, even in well-buffered seawater (Eberhard etal., 1995 Juniper Tebo, 1995). Newly formed sulphide deposits are rapidly subjected to oxidation upon contact with ambient seawater, and some show micro-scale weathering features (e.g. etch pits on mineral surfaces Verati etal., 1999),... 

Mandernack et al. (91) extended the studies of Hastings and Emerson (89) and more systematically examined the Mn oxidation state and mineralogy of the Mn oxides formed in low ionic strength buffer and in natural seawater under various environmentally-relevant temperatures and Mn(II) concentrations. Experiments were conducted with SG-1 spores in HEPES buffer and HEPES buffered seawater, at pH 7.4-8.0, in 10 pM to 10 mM Mn(II), and at 3°C, 25°C, and 50-55°C. After two... 

E. L. Shock (1990) provides a different interpretation of these results he criticizes that the redox state of the reaction mixture was not checked in the Miller/Bada experiments. Shock also states that simple thermodynamic calculations show that the Miller/Bada theory does not stand up. To use terms like instability and decomposition is not correct when chemical compounds (here amino acids) are present in aqueous solution under extreme conditions and are aiming at a metastable equilibrium. Shock considers that oxidized and metastable carbon and nitrogen compounds are of greater importance in hydrothermal systems than are reduced compounds. In the interior of the Earth, CO2 and N2 are in stable redox equilibrium with substances such as amino acids and carboxylic acids, while reduced compounds such as CH4 and NH3 are not. The explanation lies in the oxidation state of the lithosphere. Shock considers the two mineral systems FMQ and PPM discussed above as particularly important for the system seawater/basalt rock. The FMQ system acts as a buffer in the oceanic crust. At depths of around 1.3 km, the PPM system probably becomes active, i.e., N2 and CO2 are the dominant species in stable equilibrium conditions at temperatures above 548 K. When the temperature of hydrothermal solutions falls (below about 548 K), they probably pass through a stability field in which CH4 and NII3 predominate. If kinetic factors block the achievement of equilibrium, metastable compounds such as alkanes, carboxylic acids, alkyl benzenes and amino acids are formed between 423 and 293 K. 

For most organic chemicals the solubility is reported at a defined temperature in distilled water. For substances which dissociate (e.g., phenols, carboxylic acids and amines) it is essential to report the pH of the determination because the extent of dissociation affects the solubility. It is common to maintain the desired pH by buffering with an appropriate electrolyte mixture. This raises the complication that the presence of electrolytes modifies the water structure and changes the solubility. The effect is usually salting-out. For example, many hydrocarbons have solubilities in seawater about 75% of their solubilities in distilled water. Care must thus be taken to interpret and use reported data properly when electrolytes are present. 

Fletsch and Richards [51] determined fluoride in seawater spectrophotometri-cally as the cerium alizarin complex. The cerium alizarin complex and chelate was formed in 20% aqueous acetone at pH 4.35 (sodium acetate buffer) and, after 20-60 min, the extinction measured at 625 nm (2.5 cm cell) against water. The calibration graph was rectilinear for 8-200 ig/l fluoride the mean standard deviation was 10 xg/l at a concentration of 1100 ig/l fluoride. 

Ke and Regier [71] have described a direct potentiometric determination of fluoride in seawater after extraction with 8-hydroxyquinoline. This procedure was applied to samples of seawater, fluoridated tap-water, well-water, and effluent from a phosphate reduction plant. Interfering metals, e.g., calcium, magnesium, iron, and aluminium were removed by extraction into a solution of 8-hydroxyquinoline in 2-butoxyethanol-chloroform after addition of glycine-sodium hydroxide buffer solution (pH 10.5 to 10.8). A buffer solution (sodium nitrate-l,2-diamino-cyclohexane-N,N,N. AT-tetra-acetic acid-acetic acid pH 5.5) was then added to adjust the total ionic strength and the fluoride ions were determined by means of a solid membrane fluoride-selective electrode (Orion, model 94-09). Results were in close agreement with and more reproducible than those obtained after distillation [72]. Omission of the extraction led to lower results. Four determinations can be made in one hour. 

Van den Berg [131] used this technique to determine nanomolar levels of nitrate in seawater. Samples of seawater from the Menai Straits were filtered and nitrite present reacted with sulfanilamide and naphthyl-amine at pH 2.5. The pH was then adjusted to 8.4 with borate buffer, the solution de-aerated, and then subjected to absorptive cathodic stripping voltammetry. The concentration of dye was linearly related to the height of the reduction peak in the range 0.3-200 nM nitrate. The optimal concentrations of sulfanilamide and naphthyl-amine were 2 mM and 0.1 mM, respectively, at pH 2.5. The standard deviation of a determination of 4 nM nitrite was 2%. The detection was 0.3 nM for an adsorption time of 60 sec. The sensitivity of the method in seawater was the same as in fresh water. 

In the amperometric titration for the determination of total residual chlorine in seawater, tri-iodide ions are generated by the reaction between hypochlorite and/or hypobromite with excess iodide pH 4 (reactions (4.3) and (4.4)). The pH is buffered by adding a pH 4 acetic acid-sodium acetate buffer to the sample. 

Wong [8] found that the determination of residual chlorine in seawater by the amperometic titrimetic method, potassium iodide must be added to the sample before the addition of the pH 4 buffer, and the addition of these two reagents should not be more than a minute apart. Serious analytical error may arise if the order of addition of the reagents is reversed. There is no evidence suggesting the formation of iodate by the reaction between hypobromite and iodide. Concentrations of residual chlorine below 1 mg/1 iodate, which occurs naturally in seawater, causes serious analytical uncertainties. 

Howard [27] determined dissolved aluminium in seawater by the micelle-enhanced fluorescence of its lumogallion complex. Several surfactants (to enhance fluorescence and minimise interferences), used for the determination of aluminium at very low concentrations (below 0.5 pg/1) in seawaters, were compared. The surfactants tested in preliminary studies were anionic (sodium lauryl sulfate), non-ionic (Triton X-100, Nonidet P42, NOPCO, and Tergital XD), and cationic (cetyltrimethylammonium bromide). Based on the degree of fluorescence enhancement and ease of use, Triton X-100 was selected for further study. Sample solutions (25 ml) in polyethylene bottles were mixed with acetate buffer (pH 4.7, 2 ml) lumogallion solution (0.02%, 0.3 ml) and 1,10-phenanthroline (1.0 ml to mask interferences from iron). Samples were heated to 80 °C for 1.5 h, cooled, and shaken with neat surfactant (0.15 ml) before fluorescence measurements were made. This procedure had a detection limit at the 0.02 pg/1 level. The method was independent of salinity and could therefore be used for both freshwater and seawater samples. 

Salgado Ordonez et al. [28] used di-2-pyridylketone 2-furoyl-hydrazone as a reagent for the fluorometric determination of down to 0.2 pg aluminium in seawater. A buffer solution at pH 6.3, and 1 ml of the reagent solution were added to the samples containing between 0.25 to 2.50 pg aluminium. Fluorescence was measured at 465 nm, and the aluminium in the sample determined either from a calibration graph prepared under the same conditions or a standard addition procedure. Aluminium could be determined in the 10-100 pg/1 range. The method was satisfactorily applied to spiked and natural seawater samples. 

Various chromogenic reagents have been used for the spectrophotometric determination of boron in seawater. These include curcumin [108,109], nile blue [110], and more recently 3,5 di-tert butylcatechol and ethyl violet [111]. Uppstroem [108] added anhydrous acetic acid (1 ml) and propionic anhydride (3 ml) to the aqueous sample (0.5 ml) containing up to 5 mg of boron per litre as H3BO3 in a polyethylene beaker. After mixing and the dropwise addition of oxalyl chloride (0.25 ml) to catalyse the removal of water, the mixture is set aside for 15-30 minutes and cooled to room temperature. Subsequently, concentrated sulfuric-anhydrous acetic acid (1 1) (3 ml) and curcumin reagent (125 mg curcumin in 100 ml anhydrous acetic acid) (3 ml) are added, and the mixed solution is set aside for at least 30 minutes. Finally 20 ml standard buffer solution (90 ml of 96% ethanol, 180 g ammonium acetate - to destroy excess of protonated curcumin - and 135 ml anhydrous acetic acid diluted to 1 litre... 

A technique for the determination of free cupric ions in seawater has been described by Sunda and Hanson [332], The method is based on sorption of copper onto Sep-Pak Cis cartridges and internal free cupric ion calibration. Calibration is accomplished by adding cupric ion buffers and EDTA, which competes with natural organic ligands for copper complexation. The method was used to establish that 0-2% of the copper occurs as inorganic species and 98-100% occurs as organic complexes. 

Atomic absorption spectrometry coupled with solvent extraction of iron complexes has been used to determine down to 0.5 pg/1 iron in seawater [354, 355]. Hiire [354] extracted iron as its 8-hydroxyquinoline complex. The sample is buffered to pH 3-6 and extracted with a 0.1 % methyl isobutyl ketone solution of 8-hydroxyquinoline. The extraction is aspirated into an air-acetylene flame and evaluated at 248.3 nm. 

Cyclohexane-1,2-dione dioxime (nioxime) complexes of cobalt (II) and nickel (II) were concentrated from 10 ml seawater samples onto a hanging mercury drop electrode by controlled adsorption. Cobalt (II) and nickel (II) reduction currents were measured by differential pulse cathodic stripping voltammetry. Detection limits for cobalt and nickel were 6 pM and 0.45 mM, respectively. The results of detailed studies for optimising the analytical parameters, namely nioxime and buffer concentrations, pH, and adsorption potential are discussed. 

A fluorescence method that would measure either free or combined amino acids, depending upon the pH of the solution, was originally proposed by Udenfriend et al. [282] and adapted for seawater by North [283] and Packard and Dortch [284], In this Fluran method, peptides normally yield maximum fluorescence by pH 7, while amino acids fluoresce best at pH 9. With the proper choice of buffers, the fluorescence of peptides and proteins can be differentiated from that due to free amino acids. 

Samuelsen [345] has reported an HPLC method for the determination of trichlorfos and dichlorvos in seawater. A methyl cyanide phosphate buffer was used and detection was achieved by ultraviolet measurements at 205 nm. 

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