Cadmium interference

Cadmium is chemically similar to the metal zinc, and is absorbed from the gut in a similar way using the same system. It can interfere with zinc in the body and consequently may affect the male reproductive system where zinc is important. Cadmium interferes with the metabolism of calcium too, a critical mineral in the body with which it also has similarities. This interference leads to loss of calcium from the bones which then become brittle (osteomalacia). In the case of itai-itai disease, which was the result of cadmium poisoning in Japan, the exposure to cadmium was accompanied by a deficiency of vitamin D which made the problems with the bones worse. 

Since the kidneys are the main depot for cadmium, they are of greatest concern for cadmium toxicity. Cadmium interferes with the proximal tubule s reabsorption function. This leads to abnormal actions of uric acid, calcium, and phosphorus. Amino aciduria (amino acids in the urine) and glucosuria (glucose in the urine) result in later stages, proteinuria (protein in the urine) results. When this happens, it is assumed that there is a marked decrease in glomerular filtration. Long-term exposure to cadmium leads to anemia, which may result from cadmium interfering with iron absorption. 

Cadmium Interference witii ki(hiey ftinction, fume produces acute irritation of the lung. 

Plausible hypotheses to explain cadmium interference with neural tube closure may be developed on the basis of the importance of cell surface modifications and/or microfllaments and microtubules in the neurulation process, although observations bearing directly on these possibilities have yet to be reported. Virtual restriction of cadmium interference with neural tube closure to the cephalic region, however, would require additional assumptions. This suggests the likelihood that cadmium is affecting some aspect of the closure process that is either peculiar to, or of overriding importance for, closure of the cephalic neural tube. 

Cadmium is an interferant because it forms a precipitate with o-phenanthroline. What effect would the formation of a Cd-o-phenanthroline precipitate have on the determination of the parts per million of Fe in a sample ... 

Chemical Gas Detection. Spectral identification of gases in industrial processing and atmospheric contamination is becoming an important tool for process control and monitoring of air quaUty. The present optical method uses the ftir (Fourier transform infrared) interference spectrometer having high resolution (<1 cm ) capabiUty and excellent sensitivity (few ppb) with the use of cooled MCT (mercury—cadmium—teUuride) (2) detectors. 

Although the most sensitive line for cadmium in the arc or spark spectmm is at 228.8 nm, the line at 326.1 nm is more convenient to use for spectroscopic detection. The limit of detection at this wavelength amounts to 0.001% cadmium with ordinary techniques and 0.00001% using specialized methods. Determination in concentrations up to 10% is accompHshed by solubilization of the sample followed by atomic absorption measurement. The range can be extended to still higher cadmium levels provided that a relative error of 0.5% is acceptable. Another quantitative analysis method is by titration at pH 10 with a standard solution of ethylenediarninetetraacetic acid (EDTA) and Eriochrome Black T indicator. Zinc interferes and therefore must first be removed. 

Determination of copper as copper(I) thiocyanate Discussion. This is an excellent method, since most thiocyanates of other metals are soluble. Separation may thus be effected from bismuth, cadmium, arsenic, antimony, tin, iron, nickel, cobalt, manganese, and zinc. The addition of 2-3 g of tartaric acid is desirable for the prevention of hydrolysis when bismuth, antimony, or tin is present. Excessive amounts of ammonium salts or of the thiocyanate precipitant should be absent, as should also oxidising agents the solution should only be slightly acidic, since the solubility of the precipitate increases with decreasing pH. Lead, mercury, the precious metals, selenium, and tellurium interfere and contaminate the precipitate. 

Large amounts of chloride, cobalt(II), and chromium(III) do not interfere iron(III), nickel, molybdenum)VI), tungsten(VI), and uranium(VI) are innocuous nitrate, sulphate, and perchlorate ions are harmless. Large quantities of magnesium, cadmium, and aluminium yield precipitates which may co-precipitate manganese and should therefore be absent. Vanadium causes difficulties only... 

Sulphuric acid is not recommended, because sulphate ions have a certain tendency to form complexes with iron(III) ions. Silver, copper, nickel, cobalt, titanium, uranium, molybdenum, mercury (>lgL-1), zinc, cadmium, and bismuth interfere. Mercury(I) and tin(II) salts, if present, should be converted into the mercury(II) and tin(IV) salts, otherwise the colour is destroyed. Phosphates, arsenates, fluorides, oxalates, and tartrates interfere, since they form fairly stable complexes with iron(III) ions the influence of phosphates and arsenates is reduced by the presence of a comparatively high concentration of acid. 

Considerable amounts of zinc, cadmium, tin(IV), manganese(II), chromium(III), and smaller amounts of aluminium cause little or no interference at pH 2.4 the main interferences are lead(II), bismuth, cobalt(II), nickel, and copper(II). 

The detailed mechanism dictating the regulation of the process depends on the specific nature of the system, i.e., on the particular compound to be deposited, complexing agent, solution pH, film thickness, potential, etc. For example, in the case of the Cd-Se system, electroreduction of selenosulfate occurs at more positive potentials for either EDTA-ammonia- or NTA-complexed cadmium [13], whereas for ZnSe, the potential required for the reduction of selenosulfate is already reducing for zinc, implying thus a different mechanism. The metal complex has to be adequately stable and should not interfere with selenosulfate reduction. In these terms. 

Table 6.3. Spectral interferences in ICP-MS of the five most abundant cadmium isotopes relevant for the cadmium determination in Mo-Zr alloys additional Cd isotopes 106Cd 1.25%, 108Cd 0.89%, 116Cd 7.49% ...

Cadmium is nutritionally non-essential, toxic and a ubiquitous environmental pollutant. It is found in leafy vegetables, grains and cereals, and since it is present in substantial amounts in tobacco leaves, cigarette smokers on a packet a day can easily double their cadmium intake. It has a long biological half-life (17-30 years in man), accumulates in liver and kidneys and its toxicity involves principally kidney and bone (Goyer, 1997).While Cd interferes primarily with calcium, it also interacts with zinc and can induce the synthesis of metallothionein. Cadmium bound to metallothionein in liver or kidney is thought to be non-toxic, but cadmium in plasma... 

Spencer and Brewer [111] have reviewed methods for the determination of nitrate in seawater. Classical methods for determining low concentrations of nitrate in seawater use reduction to nitrite with cadmium/copper [ 112,116,117] or zinc powder [113] followed by conversion to an azo dye using N- 1-naphthyl-ethylenediamine dihydrochloride and spectrophotometric evaluation. Malho-tra and Zanoni [114] and Lambert and Du Bois [115] have discussed the interference by chloride in reduction-azo dye methods for the determination of nitrate. 

Several ions (e.g., manganese, iron (II), iron (III), cobalt, nickel, copper, zinc, cadmium, lead, and uranyl) react with pyrocatechol violet, and to some extent are extracted together with aluminium. The interferences from these ions and other metal ions generally present in seawater could be eliminated by extraction with diethyldithiocarbamate as masking agent. With this agent most of the metal ions except aluminium were extracted into chloroform, and other metal ions did not react in the amounts commonly found in seawater. Levels of aluminium between 6 and 6.3 pg/1 were found in Pacific Ocean and Japan Sea samples by this method. 

In the determination of cadmium in seawater, for both operational reasons and ease of interpretation of the results it is necessary to separate particulate material from the sample immediately after collection. The dissolved trace metal remaining will usually exist in a variety of states of complexation and possibly also of oxidation. These may respond differently in the method, except where direct analysis is possible with a technique using high-energy excitation, such that there is no discrimination between different states of the metal. The only technique of this type with sufficiently low detection limits is carbon furnace atomic absorption spectrometry, which is subject to interference effects from the large and varying content of dissolved salts. 

Campbell and Ottaway [136] also used selective volatilisation of the cadmium analyte to determine cadmium in seawater. They could detect 0.04 pg/1 cadmium (2pg in 50 pi) in seawater. They dried at 100 °C and atomised at 1500 °C with no char step. Cadmium was lost above 350 °C. They could not use ammonium nitrate because the char temperature required to remove the ammonium nitrate also volatilised the cadmium. Sodium nitrate and sodium and magnesium chloride salts provided reduced signals for cadmium at much lower concentrations than their concentration in seawater if the atomisation temperature was in excess of 1800 °C. The determination required lower atomisation temperatures to avoid atomising the salts. Even this left the magnesium interference, which required the method of additions. 

Guevremont et al. [117] studied the use of various matrix modifiers in the graphite furnace gas method of determination of cadmium in seawater. These included citric acid, lactic acid, aspartic acid, histidine, and EDTA. The addition of less than 1 mg of any of the compounds to 1 ml seawater significantly decreased matrix interference. Citric acid achieved the highest sensitivity and reduction of interference, with a detection limit of 0.01 pg cadmium per litre. 

Pruszkowska et al. [135] described a simple and direct method for the determination of cadmium in coastal water utilizing a platform graphite furnace and Zeeman background correction. The furnace conditions are summarised in Table 5.1. These workers obtained a detection limit of 0.013 pg/1 in 12 pi samples, or about 0.16 pg cadmium in the coastal seawater sample. The characteristic integrated amount was 0.35 pg cadmium per 0.0044 A s. A matrix modifier containing di-ammonium hydrogen phosphate and nitric acid was used. Concentrations of cadmium in coastal seawater were calculated directly from a calibration curve. Standards contained sodium chloride and the same matrix modifier as the samples. No interference from the matrix was observed. 

Electrothermal atomic absorption spectrophotometry with Zeeman background correction was used by Zhang et al. [141] for the determination of cadmium in seawater. Citric acid was used as an organic matrix modifier and was found to be more effective than EDTA or ascorbic acid. The organic matrix modifier reduced the interferences from salts and other trace metals and gave a linear calibration curve for cadmium at concentrations < 1.6 pg/1. The method has a limit of detection of 0.019 pg/1 of cadmium and recoveries of 95-105% at the 0.2 pg of cadmium level. 

After adjusting to 2 mol 1 1 in hydrochloric acid, 500 ml of the sample is adsorbed on a column of Dowex 1-XS resin (Cl form) and elution is then effected with 2 M nitric acid. The solution is evaporated to dryness after adding 1M hydrochloric acid, and the tin is again adsorbed on the same column. Tin is eluted with 2 M nitric acid, and determined in the eluate by the spectrophotometric catechol violet method. There is no interference from 0.1 mg of aluminium, manganese, nickel, copper, zinc, arsenic, cadmium, bismuth, or uranium any titanium, zirconium, or antimony are removed by ion exchange. Filtration of the sample through a Millipore filter does not affect the results, which are in agreement with those obtained by neutron activation analysis. 

Fang et al. [661] have described a flow injection system with online ion exchange preconcentration on dual columns for the determination of trace amounts of heavy metal at pg/1 and sub-pg/1 levels by flame atomic absorption spectrometry (Fig. 5.17). The degree of preconcentration ranges from a factor of 50 to 105 for different elements, at a sampling frequency of 60 samples per hour. The detection limits for copper, zinc, lead, and cadmium are 0.07, 0.03, 0.5, and 0.05 pg/1, respectively. Relative standard deviations are 1.2-3.2% at pg/1 levels. The behaviour of the various chelating exchangers used was studied with respect to their preconcentration characteristics, with special emphasis on interferences encountered in the analysis of seawater. 

Stein et al. [673] have described a simplified, sensitive, and rapid method for determining low concentrations of cadmium, lead, and chromium in estuarine waters. To minimise matrix interferences, nitric acid and ammonium nitrate are added for cadmium and lead only nitric acid is added for chromium. Then 10,20, or 50 pi of the sample or standard (the amount depending on the sensitivity required) is injected into a heated graphite atomiser, and specific atomic absorbance is measured. Analyte concentrations are calculated from calibration curves for standard solutions in demineralised water for chromium, or an artificial seawater medium for lead and cadmium. 

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