Natural waters seawater

Andreae [324,325] has described a gas chromatographic method for the determination of nanogram quantities of dimethyl sulfoxide in natural waters, seawater, and phytoplankton culture waters. The method uses chemical reduction with sodium borohydride to dimethyl sulfide, which is then determined gas-chromatographically using a flame photometric detector. 

Chapters 1 to 3) contains fundamental principles governing aqueous corrosion and high-temperature corrosion and covers the main environments causing corrosion such as atmospheric, natural waters, seawater, soils, concrete, as well as microbial and biofouling environments. 

Typical examples of liquid samples include those drawn from containers of commercial solvents beverages, such as milk or fruit juice natural waters, including from lakes, streams, seawater, and rain bodily fluids, such as blood and urine and, suspensions, such as those found in many oral medications. 

Dimethyl sulfoxide occurs widely at levels of <3 ppm. It has been isolated from spearmint oil, com, barley, malt, alfalfa, beets, cabbage, cucumbers, oats, onion, Swiss chard, tomatoes, raspberries, beer, coffee, milk, and tea (5). It is a common constituent of natural waters, and it occurs in seawater in the 2one of light penetration where it may represent a product of algal metaboHsm (6). Its occurrence in rainwater may result from oxidation of atmospheric dimethyl sulfide, which occurs as part of the natural transfer of sulfur of biological origin (7,8). 

Zinc, like most metals, is found in all natural waters and soils as well as the atmosphere and is an important trace element in plant and animal life (see Mineral nutrients). Rocks of various kinds contain 20—200 ppm zinc and normal soils 10—30 ppm (average ca 50 ppm) in uncontaminated areas. The average zinc content of coal is 33 ppm. Seawater contains 1—27 )-lg/L (median ca 8 p.g/L), and uncontaminated freshwater usually <10 / g/L. 

A great diversity in the concentration of dissolved organic matter also occurs in natural water. Commonly, the concentration ranges from 0.5 to 50 mg/liter. Fresh water and seawater typically have values of 0.5-1.5 mg/liter (18). 

Photolysis studies of methyl parathion have been reported. A study examining the photodegradation of methyl parathion in river and seawater at variable temperatures showed the half-lives to be 11 and 34 days, respectively (Lartiges and Garrigues 1995). During photolysis in natural water 50% of the... 

Flow injection analysis has been used for the automated determination of hydrogen sulfide in seawater [20]. A low-sensitivity flow injection analysis manifold for concentrations up to 200 imol/l hydrogen sulfide had a detection limit of 0.12 xmol/l. Sulfide standards were calibrated by colorimetric measurement of the excess tri-iodide ion remaining after reaction of sulfide with iodine. The coefficient of variation was less than 1% at concentrations greater than 10 imol/l. The method was fast, accurate, sensitive enough for most natural waters, and could be used both for discrete and continuous analysis. 

Stolzberg [143] has reviewed the potential inaccuracies of anodic stripping voltammetry and differential pulse polarography in determining trace metal speciation, and thereby bio-availability and transport properties of trace metals in natural waters. In particular it is stressed that nonuniform distribution of metal-ligand species within the polarographic cell represents another limitation inherent in electrochemical measurement of speciation. Examples relate to the differential pulse polarographic behaviour of cadmium complexes of NTA and EDTA in seawater. 

Ruzic [278 ] considered the theoretical aspects of the direct titration of copper in seawaters and the information this technique provides regarding copper speciation. The method is based on a graph of the ratio between the free and bound metal concentration versus the free metal concentration. The application of this method, which is based on a 1 1 complex formation model, is discussed with respect to trace metal speciation in natural waters. Procedures for interpretation of experimental results are proposed for those cases in which two types of complexes with different conditional stability constants are formed, or om which the metal is adsorbed on colloidal particles. The advantages of the method in comparison with earlier methods are presented theoretically and illustrated with some experiments on copper (II) in seawater. The limitations of the method are also discussed. 

Gill and Fitzgerald [481] determined picomolar quantities of mercury in seawater using stannous chloride reduction and two-stage amalgamation with gas-phase detection. The gas flow system used two gold-coated bead columns (the collection and the analytical columns) to transfer mercury into the gas cell of an atomic absorption spectrometer. By careful control and estimation of the blank, a detection limit of 0.21 pM was achieved using 21 of seawater. The accuracy and precision of this method were checked by comparison with aqueous laboratory and National Bureau of Standards (NBS) reference materials spiked into acidified natural water samples at picomolar levels. Further studies showed that at least 88% of mercury in open ocean and coastal seawater consisted of labile species which could be reduced by stannous chloride under acidic conditions. 

Wrembel and Pajak [486] evaporated mercury from natural water samples with argon and amalgamated the mercury with a gold foil. The mercury was excited in a ring-discharge plasma and determined by atomic emission spectroscopy. The method was applied to the determination of mercury in seawater in the range 0.01-1.0 xg/l. 

Kawabuchi and Kuroda have concentrated molybdenum by anion exchange from seawater containing acid and thiocyanate [497] or hydrogen peroxide [497,498], and determined it spectrophotometrically. Korkisch et al. [499] concentrated molybdenum from natural waters on Dowex 1-X8 in the presence of thiocyanate and ascorbic acid. 

Hidalgo et al. [509] reported a method for the determination of molybdenum (VI) in natural waters based on differential pulse polarography. The catalytic wave caused by molybdenum (VI) in nitrate medium following preconcentration by coflotation on ferric hydroxide was measured. For seawater samples, hexadecyltrimethylammomum bromide with octadecylamine was used as the surfactant. The method was applied to molybdenum in the range 0.7-5.7 Xg/l. 

The concentration of nickel in natural waters is so low that one or two enrichment steps are necessary before instrumental analysis. The most common method is graphite furnace atomic absorption after preconcentration by solvent extraction [122] or coprecipitation [518]. Even though this technique has been used successfully for the nickel analyses of seawater [519,520] it is vulnerable to contamination as a consequence of the several manipulation steps and of the many reagents used during preconcentration. 

Andreae [564] coprecipitated tellurium (V) and tellurium (VI) from seawater and other natural waters with magnesium hydroxide. After dissolution of the precipitate with hydrochloric acid, the tellurium (IV) was reduced to tellurium hydride in 3 M hydrochloric acid. The hydride was trapped inside the graphite tube of a graphite furnace atomic absorption spectrometer, heated to 300 °C, and tellurium (IV) determined. Tellurium (VI) was reduced to tellurium (IV) by boiling with hydrochloric acid and total tellurium determined. Tellurium (VI) was then calculated. The limit of detection was 0.5 pmol per litre and precision 10-20%. 

Although anodic stripping voltammetry is one of the few techniques suitable for the direct determination of heavy metals in natural waters [310,756-764], it is not readily adaptable to in situ measurements. Lieberman and Zirino [623] examined a continuous flow system for the anodic stripping voltammetry determination of zinc in seawater, using a tubular graphite electrode predeposited with mercury. A limitation of the approach was the need to pump seawater to the measurement cell, while the method required the removal of oxygen with nitrogen before measurements. 

Bott [790] reviewed of voltammetric methods for the determination of trace metals in seawater and other natural waters. 

Blumer M (1970) Dissolved organic compounds in seawater. Saturated and olefinic hydrocarbons and singly branched fatty acids. In Hood DW (ed) Organic matter in natural waters. Publication no. 1. Institute of Marine Science, University of Alaska, pp 153-167... 

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