Seawater molybdenum

Isaeva [181] described a phosphomolybdate method for the determination of phosphate in turbid seawater. Molybdenum titration methods are subject to extensive interferences and are not considered to be reliable when compared with more recently developed methods based on solvent extraction [182-187], such as solvent-extraction spectrophotometric determination of phosphate using molybdate and malachite green [188]. In this method the ion pair formed between malachite green and phosphomolybdate is extracted from the seawater sample with an organic solvent. This extraction achieves a useful 20-fold increase in the concentration of the phosphate in the extract. The detection limit is about 0.1 ig/l, standard deviation 0.05 ng-1 (4.3 xg/l in tap water), and relative standard deviation 1.1%. Most cations and anions found in non-saline waters do not interfere, but arsenic (V) causes large positive errors. 

Nickel is usually alloyed with elements including copper, chromium, molybdenum and then for strengthening and to improve corrosion resistance for specific applications. Nickel-copper alloys (and copper-nickel alloys see Section 53.5.4) are widely used for handling water. Pumps and valve bodies for fresh water, seawater and mildly acidic alkaline conditions are made from cast Ni-30% Cu type alloys. The wrought material is used for shafts and stems. In seawater contaminated with sulfide, these alloys are subject to pitting and corrosion fatigue. Ammonia contamination creates corrosion problems as for commercially pure nickel. 

The addition of chromium forms a family of Ni-Cr-Mo alloys such as Hastelloy alloys C-276, C-22, and C-2000. These alloys contain 16 to 22 percent chromium and 13 to 16 percent molybdenum and are very resistant to a wide variety of chemical environments. They are considered resistant to stress-corrosion cracking and very resistant to localized corrosion in chloride-containing environments. These alloys are resistant to strong oxidizing solutions, such as wet chlorine and hypochlorite solutions. They are among only a few alloys that are completely resistant to seawater. The carbon contents are low enough that weld sensitization is not a problem during fabrication. These alloys are also more difficult to machine than stainless steel, but fabrication is essentially the same. 

Emerson SR, Huested SS (1991) Ocean anoxia and the concentrations of molybdenum and vanadium in seawater. Marine Chem 34 177-196... 

A limited amount of work has been carried out on the determination of molybdenum in seawater by AAS [107-109] and graphite furnace atomic absorption spectrometry [110]. In a recommended procedure a 50 ml sample at pH 2.5 is preconcentrated on a column of 0.5 gp-aminobenzylcellulose, then the column is left in contact with 1 mol/1 ammonium carbonate for 3 h, after which three 5 ml fractions are collected. Finally, molybdenum is determined by AAS at 312.2 nm with use of the hot-graphite-rod technique. At the 10 mg/1 level the standard deviation was 0.13 xg. 

A commonly used procedure for the determination of phosphate in seawater and estuarine waters uses the formation of the molybdenum blue complex at 35-40 °C in an autoanalyser and spectrophotometric evaluation of the resulting colour. Unfortunately, when applied to seawater samples, depending on the chloride content of the sample, peak distortion or even negative peaks occur which make it impossible to obtain reliable phosphate values (Fig. 2.7). This effect can be overcome by the replacement of the distilled water-wash solution used in such methods by a solution of sodium chloride of an appropriate concentration related to the chloride concentration of the sample. The chloride content of the wash solution need not be exactly equal to that of the sample. For chloride contents in the sample up to 18 000 mg/1 (i.e., seawater),... 

Eberlein and Kattner [194] described an automated method for the determination of orthophosphate and total dissolved phosphorus in the marine environment. Separate aliquots of filtered seawater samples were used for the determination orthophosphate and total dissolved phosphorus in the concentration range 0.01-5 xg/l phosphorus. The digestion mixture for total dissolved phosphorus consisted of sodium hydroxide (1.5 g), potassium peroxidisulfate (5 g) and boric acid (3 g) dissolved in doubly distilled water (100 ml). Seawater samples (50 ml) were mixed with the digestion reagent, heated under pressure at 115-120 °C for 2 h, cooled, and stored before determination in the autoanalyser system. For total phosphorus, extra ascorbic acid was added to the aerosol water of the autoanalyser manifold before the reagents used for the molybdenum blue reaction were added. For measurement of orthophosphate, a phosphate working reagent composed of sulfuric acid, ammonium molyb-... 

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]. 

Marcantoncetos et al. [112] have described a phosphorimetric method for the determination of traces of boron in seawater. This method is based on the observation that in the glass formed by ethyl ether containing 8% of sulfuric acid at 77 K, boric acid gives luminescent complexes with dibenzoylmethane. A 0.5 ml sample is diluted with 10 ml 96% sulfuric acid, and to 0.05-0.3 ml of this solution 0.1ml 0.04 M dibenzoylmethane in 96% sulfuric acid is added. The solution is diluted to 0.4 ml with 96% sulfuric acid, heated at 70 °C for 1 h, cooled, ethyl ether added in small portions to give a total volume of 5 ml, and the emission measured at 77 K at 508 nm, with excitation at 402 nm. At the level of 22 ng boron per ml, hundredfold excesses of 33 ionic species give errors of less than 10%. However, tungsten and molybdenum both interfere. 

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. 

In a method described by Kiriyama and Kuroda [500], molybdenum is sorbed strongly on Amberlite CG 400 (Cl form) at pH 3 from seawater containing ascorbic acid, and is easily eluted with 6 M nitric acid. Molybdenum in the effluent can be determined spectrophotometrically with potassium thiocyanate and stannous chloride. The combined method allows selective and sensitive determination of traces of molybdenum in seawater. The precision of the method is 2% at a molybdenum level of 10 xg/l. To evaluate the feasibility of this method, Kiriyama and Kuroda [500] spiked a known amount of molybdenum and analysed it by this procedure. The recoveries for 4 to 8 xg molybdenum added to 500 or 1000 ml samples were between 90 and 100%. 

Nakahara and Chakrabarti [137] showed that the seawater salt matrix can be removed from the sample by selective volatilisation at 1700-1850 °C, but the presence of sodium chloride, sodium sulfate, and potassium chloride causes a considerable decrease in molybdenum absorbance, and magnesium chloride and calcium chloride cause a pronounced enhancement. The presence of magnesium chloride prevents the depressive effects. Samples of less than 50 pi can be analysed directly without using a background corrector with a precision of 10%. 

These workers conclude that the selective volatilisation technique is highly suitable for the determination of traces of molybdenum in synthetic (and most probably real) seawater samples. It has the advantages of freedom from contamination and loss during sample preparation and is faster, and cheaper, than procedures using separations. 

The sensitivity achieved should enable seawater samples to be analysed for molybdenum, because the concentration of molybdenum in seawater is usually 2.1 -18.8 pg/1. The selected temperature of 1700-1850 °C during the charring stage permits separation of the seawater matrix from the analyte prior to atomisation with the Perkin-Elmer Model 603 atomic absorption spectrometer equipped with a heated graphite atomiser (HGA-2100). 

Kuroda et al. [505] determined traces of molybdenum in seawater by combined anion exchange and graphite-furnace atomic absorption spectrometry. 

Trace amounts of molybdenum were concentrated from acidified seawater on a strongly basic anion exchange resin (Bio-Rad AG1 X-8 in the chloride form) by treating the water with sodium azide. Molybdenum (VI) complexes with azide were stripped from the resin by elution with ammonium chlo-ride/ammonium hydroxide solution (2 M/2 M). Relative standard deviations of better than 8% at levels of 10 xg per litre were attained for seawater using graphite furnace atomic absorption spectrometry. 

Specht and Beauchemin [506] have described an automated system to provide online addition of isotopic spikes to seawater samples in the determination of molybdenum by inductively coupled plasma mass spectrometry. 

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. 

Van den Berg [510] carried out direct determinations of molybdenum in seawater by adsorption voltammetry. The method is based on complex formation of molybdenum (VI) with 8-hydroxyquinoline (oxine) on a hanging mercury drop electrode. The reduction current of adsorbed complexions was measured by differential pulse adsorption voltammetry. The effects of variation of pH and oxine concentration and of the adsorption potential were examined. The method was accurate up to 300 nmol/1. The detection limit was 0.1 nmol/1. 

Willie et al. [508] used Unear sweep voltammetry for the determination of molybdenum. The molybdenum was adsorbed as the Eriochrome Blue Black R complex on a static mercury drop electrode. The method was reported to have a limit of detection of 0.50 xg/l and the results agreed well with certified values for two reference seawater samples. 

Hua et al. [507] described an automated method for determination of molybdenum in seawater by means of constant-current reduction of the adsorbed 8-quinolinol complex in a computerised flow potentiometric stripping analyser. The complex was adsorbed onto a molybdenum film electrode at -0.2 V and stripped at -0.42 V. The authors report measuring molybdenum at 8.9 1.3 xg/l in reference seawater NASS-1, with a certified value of 11.5 1.9 xg/l. 

X-ray fluorescence was used for the determination of molybdenum in seawater in a method described by Kimura et al. [511]. Molybdenum is coprecipitated with sodium diethyldithiocarbamate, which is measured by X-ray fluorescence. They report a detection limit of 0.3 xg/l and a relative standard deviation of 2.9%. 

Various other techniques have been used to determine molybdenum, including adsorption voltammetry [510], electron-paramagnetic resonance spectrometry [512], and neutron activation analysis [513,514]. EPR spectrometry is carried out on the isoamyl alcohol soluble Mo(SCN)s complex and is capable of detecting 0.46 mg/1 molybdenum in seawater. Neutron activation is carried out on the /J-naphlhoin oxime [514] complex and the pyrrolidone dithiocar-bamate and diethyldithiocarbamate complex [513]. The neutron activation analysis method [514] was capable of determining down to 0.32 xg/l of molybdenum in seawater. 

Monien et al. [515] have compared results obtained in the determination of molybdenum in seawater by three methods based on inverse voltammetry, atomic absorption spectrometry, and X-ray fluorescence spectroscopy. Only the inverse voltammetric method can be applied without prior concentration of molybdenum in the sample, and a sample volume of only 10 ml is adequate. Results of determinations by all three methods on water samples from the Baltic Sea are reported, indicating their relative advantages with respect to reliability. 

Shriadah et al. [516] determined molybdenum VI in seawater by densitometry after enrichment as the Tiron complex on a thin layer of anion exchange resin. There were no interferences from trace elements or major constituents of seawater, except for chromium and vanadium. These were reduced by the addition of ascorbic acid. The concentration of dissolved molybdenum (VI) determined in Japanese seawater was 11.5 pg/1, with a relative standard deviation of 1.1%. 

An adsorbing colloid formation method has been used to separate molybdenum from seawater prior to its spectrophotometric determination by the thiocyanate procedure [517]. 

Koide et al. [537] have described a graphite furnace atomic absorption method for the determination of rhenium at picomolar levels in seawater and parts-per-billion levels in marine sediments, based upon the isolation of heptavalent rhenium species upon anion exchange resins. All steps are followed with 186-rhenium as a yield tracer. A crucial part of the procedure is the separation of rhenium from molybdenum, which significantly interferes with the graphite furnace detection when the Mo Re ratio is 2 or greater. The separation is accomplished through an extraction of tetraphenylarsonium perrhenate into chloroform, in which the molybdenum remains in the aqueous phase. 

Jin [666] used ammonium pyrrolidine dithiocarbamate and electrothermal atomic absorption spectrometry to determine lead, cadmium, copper, cobalt, tin, and molybdenum in seawater. 

Tominaga et al. [682,683] studied the effect of ascorbic acid on the response of these metals in seawater obtained by graphite-furnace atomic absorption spectrometry from standpoint of variation of peak times and the sensitivity. Matrix interferences from seawater in the determination of lead, magnesium, vanadium, and molybdenum were suppressed by addition of 10% (w/v) ascorbic acid solution to the sample in the furnace. Matrix effects on the determination of cobalt and copper could not be removed in this way. These workers propose a direct method for the determination of lead, manganese, vanadium, and molybdenum in seawater. 

Murthy and Ryan [823] used colloid flotation as a means of preconcentration prior to neutron activation analysis for arsenic, molybdenum, uranium, and vanadium. Hydrous iron (III) oxide is floated in the presence of sodium decyl sulfate with small nitrogen bubbles from 1 litre of seawater at pH 5.7. Recoveries of arsenic, molybdenum, and vanadium were better than 95%, whilst that of uranium was about 75%. 

Korkisch and Koch [106,107] determined low concentrations of uranium in seawater by extraction and ion exchange in a solvent system containing trioctyl phosphine oxide. Uranium is extracted from the sample solution (adjusted to be 1 M in hydrochloric acid and to contain 0.5% of ascorbic acid) with 0.1 M trioctylphos-phine oxide in ethyl ether. The extract is treated with sufficient 2-methoxyethanol and 12 M hydrochloric acid to make the solvent composition 2-methoxyethanol-0.1 M ethereal trioctylphosphine acid-12 M hydrochloric acid (9 10 1) this solution is applied to a column of Dowex 1-X8 resin (Cl" form). Excess of trioctylphosphine oxide is removed by washing the column with the same solvent mixture. Molybdenum is removed by elution with 2-methoxyethanol-30% aqueous hydrogen peroxide-12 M hydrochloric... 

In the method for [17] inorganic arsenic the sample is treated with sodium borohydride added at a controlled rate (Fig. 10.1). The arsine evolved is absorbed in a solution of iodine and the resultant arsenate ion is determined photometrically by a molybdenum blue method. For seawater the range, standard deviation, and detection limit are 1—4 xg/l, 1.4%, and 0.14 pg/1, respectively for potable waters they are 0-800 pg/1, about 1% (at 2 pg/1 level), and 0.5 pg/1, respectively. Silver and copper cause serious interference at concentrations of a few tens of mg/1 however, these elements can be removed either by preliminary extraction with a solution of dithizone in chloroform or by ion exchange. 

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... 

A significant proportion of the needs for reference materials for seawater trace metal studies would be addressed by the preparation of these materials. Although the total iron concentration of these reference materials should be provided, these materials clearly will be useful for studies of other important metals such as zinc, manganese, copper, molybdenum, cobalt, vanadium, lead, aluminum, cadmium, and the rare earth elements. With careful planning, such water samples should be useful for analysis of dissolved organic substances as well. The collection sites should be chosen carefully to provide both a high and a low concentration reference material for as many metals as possible. 

Molybdenum isotope variations appear to be on the order of 3.5%o in Mo/ Mo ratios, where the largest fractionation is seen between aqueous Mo in seawater and that incorporated in Fe-Mn crusts and nodules on the seafloor (Chapter 12 Anbar 2004). This isotopic contrast is interpreted to reflect fractionation by Mo sorption to Mn oxide-rich sediments relative to aqueous Mo. The 5 Mo values for euxinic sediments in turn are distinct from those of Fe-Mn crusts, highlighting the isotopic contrasts between major repositories of Mo in surface and near-surface environments. As discussed by Anbar (2004) in Chapter 12, a major focus of research on Mo isotopes has been the potential use as a paleoredox indicator in marine systems. 

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