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Aluminum-binding serum proteins: desferrioxamine alters serum aluminum speciation.

The aluminum content of four size classes of protein (high and low molecular weight, transferrin/albumin and a fraction provisionally termed albindin) in sera from healthy volunteers (group I) and from aluminum workers with normal (group II) and high (group III) total serum aluminum was compared using size exclusion chromatography and electrothermal atomic absorption spectroscopy. In the absence of any drug treatment the transferrin/albumin fraction was the major carrier, containing 29% to 33% of the aluminum recovered, in all three subject groups. Desferrioxamine treatment of groups II and III significantly decreased the proportion of aluminum bound by albumin/transferrin (P less than 0.05 in group III) and increased that bound by albindin (P less than 0.05 in groups II and III). The albindin fraction contained over 40% of the aluminum recovered from sera of group III subjects during desferrioxamine treatment. We conclude that the albindin fraction contains a protein or proteins that can form stable complexes with aluminum which may be important in preventing aluminum toxicity.

Adult↗

Supercritical fluid extraction of organotins from biological samples and speciation by liquid chromatography and inductively coupled plasma mass spectrometry.

Supercritical fluid extraction is used to extract tributyltin and triphenyltin from biological samples. The extraction conditions with carbon dioxide as supercritical fluid (methanol modifier used) are optimized for the organotins from fish tissue certified reference material. The total extraction time is found to be approximately 15 min. The recovery studies at the optimal conditions shows a recovery of 44% for tributyltin and 23% for triphenyltin. The reproducibilities for both the compounds extracted are within 2% R.S.D. The optimum conditions obtained are also used to extract tributyltin and triphenyltin from tuna fish obtained from a local grocery store.

Animals↗

Speciation of inorganic and organotin compounds in biological samples by liquid chromatography with inductively coupled plasma mass spectrometric detection.

This paper describes the effect of inorganic tin chloride on the separation of trimethyl-, tributyl- and triphenyltin-chlorides by reversed-phase ion-pair high-performance liquid chromatography with detection by inductively coupled plasma mass spectrometry. The detection limits are 1.6 pg, 1.5 pg and 2.3 pg as tin for trimethyltin, tributyltin and triphenyltin, respectively. The relative standard deviation for ten injections of 20 ng of the tin compounds was less than 5%. Inorganic tin was held strongly on the columns used, to a greater extent on the silica column compared to the polymer column. Extraction and determination of tributyltin and triphenyltin as chlorides in fish tissue (certified reference material) and tuna fish (grocery store) were performed. The recovery study from fish tissue showed an efficiency of over 90% for both tributyltin and triphenyltin and over 60% recovery for spiked tuna.

Animals↗

Arsenic speciation by micellar liquid chromatography with inductively coupled plasma mass spectrometric detection.

Four environmentally and biologically important arsenic species, dimethylarsenic acid (DMA), monomethylarsonic acid (MMA), As(III) and As(V) are separated by micellar liquid chromatography. Linear dynamic ranges for the four species are three orders of magnitude and detection limits are in the picogram range with inductively coupled plasma mass spectrometric (ICP-MS) detection. This paper discussed in detail the development of the chromatographic conditions. The micellar mobile phase, which consisted of 0.05 M cetyltrimethylammonium bromide, 10% propanol and 0.02 M borate buffer, showed good compatibility with ICP-MS. This method allowed direct injection of urine samples onto the chromatographic system without extensive pretreatment and presented no interference from chlorine in the matrix. Detection limits are comparable with other LC-ICP-MS studies. An SRM urine sample was used to demonstrate the applicability of this technique to "real-life" situations. Results indicated that DMA, MMA and As(V) were present in the urine sample.

Arsenicals↗

Chromium speciation by anion-exchange high-performance liquid chromatography with both inductively coupled plasma atomic emission spectroscopic and inductively coupled plasma mass spectrometric detection.

Development of a new method for the determination of Cr(III) and Cr(VI) is described. Anion-exchange high-performance liquid chromatography (HPLC) was used to separate Cr(III) and Cr(VI) with on-line detection by inductively coupled plasma atomic emission spectroscopy (ICP-AES) at 2766 A in preliminary studies, and inductively coupled plasma mass spectrometry (ICP-MS) with single-ion monitoring at m/z 52 and m/z 53 for final work. A mobile phase consisting of ammonium sulfate and ammonium hydroxide was used, and a simple chelation procedure with EDTA was followed to stabilize the Cr(III) species in standard solutions. ICP-MS results indicated the feasibility of using chromium isotope m/z 53 instead of the more abundant m/z 52 isotope due to a high mobile-phase background most significantly from the SO+ polyatomic interference. The absolute detection limits based on peak-height calculations were 40 pg for Cr(III) and 100 pg for Cr(VI) in aqueous media by HPLC-ICP-MS. The linear dynamic range extended from 5 ppb (ng/ml) to 1 ppm (micrograms/ml) for both species. By HPLC-ICP-AES, detection limits were 100 ng for Cr(III) and 200 ng for Cr(VI). Cr(III) was detected in NIST-SRM 1643c (National Institute of Standards and Technology-Standard Reference Material, Trace Elements in Water) by HPLC-ICP-MS at the 20 ppb level.

Chromatography, High Pressure Liquid↗

Evidence for horizontal gene transfer in Escherichia coli speciation.

After extracting more than 780 identified Escherichia coli genes from available data libraries, we investigated the codon usage of the corresponding coding sequences and extended the study of gene classes, thus obtained, to the nature and intensity of short nucleotide sequence selection, related to constraints operating at the nucleotide level. Using Factorial Correspondence Analysis we found that three classes ought to be included in order to match all data now available. The first two classes, as known, encompass genes expressed either continuously at a high level, or at a low level and/or rarely; the third class consists of genes corresponding to surface elements of the cell, genes coming from mobile elements as well as genes resulting in a high fidelity of DNA replication. This suggests that bacterial strains cultivated in the laboratory have been fixed by specific use of antimutator genes that are horizontally exchanged.

Amino Acids↗

The use of paraffin wax metabolism in the speciation of Mycobacterium avium-intracellulare.

Paraffin-wax utilisation or baiting of Mycobacterium avium-intracellulare (MAI) complex organisms and other 'atypical mycobacteria' and the inability of Mycobacterium tuberculosis to utilise paraffin are known and useful if forgotten facts. Strains of possible AIDS-related MAI have been introduced into Czapek broth devoid of any carbon source other than paraffin-wax coated slides. Replicate slides showing 'in situ' growth were subjected to the following battery of tests: acid alcohol fast staining and microscopic examination of 'in situ' growth, tellurite reduction in 3 days, absence of urea hydrolysis, inability to reduce nitrates and inability to hydrolyse Tween 80. The system has been utilised to isolate and identify MAI organisms in blood from AIDS patients. The simplicity, low cost, and reduced risk of contamination make the system especially suitable for small rural laboratories and field stations as well as laboratories in developing countries.

Acquired Immunodeficiency Syndrome↗

Speciation of organotin and organolead compounds in drinking water by gas chromatography--atomic emission spectrometry.

Raw and treated water samples and distribution system water samples were collected in forty-five Canadian municipalities for the analysis of organotin and organolead compounds. After extraction from the water samples organotin and organolead compounds were alkylated with pentylmagnesium bromide and butylmagnesium chloride respectively and analysed by gas chromatography-microwave induced plasma atomic emission spectrometry (GC-AED) using wavelengths specific for tin (326.23 nm) and lead 405.78 nm). The GC-AED system was optimised for trace level analysis, especially for organolead compounds. Organotin compounds, mainly methyltin and butyltin at concentrations up to 22 ng Sn/L and 43.6 ng Sn/L respectively, were detected in distributed water samples from six municipalities. No organotin compounds were detected in raw water samples indicating that the organotin compounds were leaching into the water from some component of the distribution system. One raw water sample contained six organolead compounds at concentrations from 0.5 to 10 ng Pb/L and five raw water and three distributed water samples contained trace levels ( < 0.5 ng Pb/L) of organolead compounds. Due to the lack of authentic standards the identity of the organolead compounds could not be confirmed by gas-chromatography mass-spectrometry.

Canada↗

The speciation of plutonium in foodstuffs and its influence on gut uptake.

Soluble plutonium complexing agents in foodstuffs have been identified. These have been labelled to high specific activity with 238Pu and their gut uptake determined in rats. The range of values found for naturally-occurring complexes was between 0.03% for oxalate and 0.1% for phytate. However, reasons are advanced for believing that the enhancement of uptake in rats fed the phytate complex would not be expected to occur in man. These results are not taken, therefore, as suggesting that there should be any change in the gut uptake factor of 0.05% currently recommended by the National Radiological Protection Board for plutonium contained in foodstuffs eaten by humans.

6-Phytase↗

Speciation studies of serum aluminum/citrate complex by liquid chromatography-furnace AAS.

We examined, in chronic-haemodialysis patients, the in vitro effect of citrate on aluminum binding to plasma proteins, desferrioxamine, and other constituents, by gel filtration chromatography. The elution profile of these complexes was studied by equilibrium and fast-protein liquid chromatography. The aluminum distribution was determined by graphite furnace atomic absorption spectrometry. We found that citrate mobilized aluminum from plasma binding sites to form an aluminum-citrate complex, possibly of colloidal nature.

Aluminum↗

Chemical speciation and distribution of arsenic in water, suspended solids and sediment of Xiangjiang River, China.

The forms of arsenic in the Zuzou Zone of the Xiangjang River are evaluated. Nine fractions of arsenic, consisting of soluble arsenic(III) and total soluble arsenic, loosely bound arsenic, aluminium arsenate, iron arsenate, calcium arsenate, arsenic occluded on iron oxide, organic compounds of arsenic and residual arsenic, were separated from suspended solids and sediments by sequential chemical extraction. All arsenic fractions were determined by ASV and AFS. The distributions of arsenic and arsenic fractions in water, sediments and suspended solids are discussed in terms of the mechanisms of arsenic transport and deposition in aquatic ecosystems.

Arsenic↗

Influence of complexing agents and surfactants on metal speciation analysis in road runoff.

A combination of medium exchange and sample acidification techniques is used to enable the calculation of the individual effects of complexing agents and surfactants on the deposition and stripping steps in anodic stripping voltammetry for copper, lead and cadmium in road and urban runoff. A simple acidification procedure is presented for determination of the toxic fraction.

Benzopyrans↗

Speciation of plutonium in potato and the gastrointestinal transfer of plutonium and americium from potato.

Complexation of Pu(IV) and Am(III) by naturally occurring agents such as citrate and phytate might enhance their uptake from the digestive tract. However, the extent to which they enhance the gastrointestinal uptake of actinides from foodstuffs is far from resolved, as this study shows. Investigations of the chemical forms of Pu(IV) and Am(III), by gel permeation chromatography, in simulated digests of potato tubers naturally radiolabelled with 239Pu(IV) and 241Am(III) have shown that neither citrate nor phytate appear to determine their chemical forms. Therefore, it is possible that these are not the complexing anions which determine the gastrointestinal transfer of these radioelements from potato meal. Isotachophoretic analyses of the juices pressed from tubers and solutions prepared by simulated digestion of potato tubers have demonstrated the presence of several low molecular weight anions. These anions might be complexing agents because they possess an isotachophoretic mobility similar to that of citrate; some of these anions remain unidentified. Whereas 239Pu and 241Am were used in the foregoing studies, 238Pu and 241Am were used to produce either in vitro or naturally radiolabelled potatoes for gastrointestinal transfer measurements using rats and hamsters. Gastrointestinal transfer values of 0.13 +/- 0.05% (mean +/- standard error of mean) and 0.16 +/- 0.06% were determined with rats for the uptake of 238Pu and 241Am, respectively, from naturally labelled potato meal. Higher gastrointestinal transfer values were obtained for hamsters: for 238Pu and 241Am the transfer values from naturally labelled meal were 0.25 +/- 0.08% and 0.33 +/- 0.07%, respectively. Similar values were observed for uptake from in vitro labelled potato meal. On the basis of the similarity of the values for the naturally labelled potato meal and for the 'spiked' potato meal it would appear that biological incorporation is not necessary for the binding of the actinides to the ligands which will determine gastrointestinal transfer.

Americium↗

Organomercury determination in biological reference materials: application to a study on mercury speciation in marine mammals off the Faröe Islands.

The potential use of graphite furnace atomic absorption spectrometry (GF-AAS) for the organic mercury determination in marine biological tissues was evaluated. Following its isolation by acid extraction in toluene, organic mercury was recovered in aqueous thiosulfate and measured by GF-AAS. The detection limit was 0.01 microgram Hg/g (as methyl mercury). Analyses were conducted on three reference standard materials certified for their methyl mercury content, DOLT-1, DORM-1, and TORT-1, provided by the National Research Council of Canada. The method resulted in very good recovery and reproducibility, indicating that GF-AAS can provide results comparable to those obtained by using more expensive and time consuming analytical techniques. The method was applied to the analysis of liver tissues of pilot whale specimens (Globicephala melas) from the drive fishery of the Faröe Islands (northeast Atlantic). The results provided useful information on the proportion of different mercury forms in the liver of these marine mammals.

Animals↗