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Chemical speciation of nickel in fly ash by phase separation and carbon paste electrode voltammetry

In a risk-based approach to cost-effective management of power plant emissions, chemical speciation of fly ash is required. A quantitative but indirect separation of nickel phases by sequential extraction was undertaken in conjunction with direct analysis of the sulfidic nickel phase by carbon paste electrode voltammetry (CPEV). Four ash samples produced in a laboratory combustion system from burning high- and low-sulfur residual oil at excess O(2) of 1 and 2-3 mol% were studied. The extractions yielded five phases of nickel. The CPEV analysis of sulfidic nickel in the ash and extraction residues was performed in pH 5 acetate. The anodic peak (-0.1 V) unique to Ni(3)S(2), distinguishing it from NiS and NiS(2), was found to be absent from these ash samples. The CPEV method was consistent with phase extraction, which showed NiSO(4) being predominant with very low proportions of sulfidic nickel.

Journal Article↗

Maintenance of species identity and controlling speciation of bacteria: a new function for restriction/modification systems?

Bacteria frequently exchange DNA among each other by horizontal gene transfer. However, maintenance of species identity and in particular speciation requires a certain barrier against an unregulated uptake of foreign DNA. Here it is suggested that formation of such a barrier is one important biological function of restriction/modification systems, in addition to the classical function of protection of bacteria against bacteriophage infection. This model explains the extreme variability and wide distribution of restriction/modification systems among prokaryotes, the prevalence of RM-systems in pathogenic bacteria and the existence of several RM-systems in single bacterial strains.

Bacteria↗

Effects of dietary folate intake and folate binding protein-1 (Folbp1) on urinary speciation of sodium arsenate in mice.

In most mammalian species, arsenic biotransformation occurs primarily by biomethylation with dimethylarsinic acid being the predominant metabolite excreted in the urine. Folbp1 (folate binding protein-1) mediated intracellular folate uptake is one route by which cells harvest folate cofactors. In light of the likely relationship between folate biochemistry and arsenic biotransformation, our experiments were designed to test: (1) whether Folbp1 is an important determinant in arsenic biotransformation, by performing urinary arsenic speciation in Folbp1 nullizygous (Folbp1(-/-)) and wildtype control mice, and (2) whether dietary folate deficiency alters arsenic biotransformation in these mice. Compared to normal folate intake, folate deficiency caused lower amounts of arsenic to be excreted in the urine of both the wildtype controls and Folbp1(-/-) mice. Folbp1(-/-) mice excreted more dimethylarsinic acid than wildtype control mice during folate deficiency, but not during normal folate intake. The present data suggest that inadequate folate intake may result in decreased biotransformation and excretion of arsenic, which is likely to increase arsenic exposure and related toxicities.

Animals↗

Speciation and metabolism of selenium injected with 82Se-enriched selenite and selenate in rats.

Selenate and selenite injected intravenously into rats were speciated by the HPLC-ICP MS method with use of an enriched stable isotope as the tracer. In dose-relation experiments, 82Se-enriched selenate or selenite was injected intravenously into male Wistar rats of 8 weeks of age (three rats/group) at single doses of 10, 25, 50, 100 and 200 microg/kg body weight for the selenate group, and 2, 5, 10, 25 and 50 microg/kg body weight for the selenite group. The animals were sacrificed 1 or 24 h later, and the concentrations and distributions of 82Se in the liver, kidneys, serum, and urine remaining in the bladder or 24-h urine were determined. In time-course experiments, 82Se-enriched selenate and selenite were injected at doses of 50 and 10 microg/kg body weight, respectively, and the animals were sacrificed 5, 15, 30, 60 and 180 min later. It was suggested that selenate is directly taken up by the liver with an efficiency of approximately 1/2 compared with selenite, the latter being taken up by the liver after being metabolized to selenide in red blood cells. Although selenate and selenite were metabolized differently in the bloodstream, and also a part of only selenate was excreted directly into the urine, the 82Se taken up by the liver was shown to be metabolized in a manner indistinguishable between selenate and selenite. 82Se of selenite origin but not of selenate origin was suggested to undergo redox reaction in the bloodstream. These results suggest that although parenteral selenate is utilized less efficiently by the body, it is utilized in the liver in a similar manner to selenite much more safely.

Animals↗

Speciation of ionic alkyllead compounds in human urine by gas chromatography-mass spectrometry after butylation through a Grignard reaction.

One analytical procedure for the determination of ionic alkyllead in human urine has been studied. The system consists of the extraction of Me3Pb+, Et3Pb+ and Pb2+ at pH 9.0 with diethyldithiocarbamate to an organic phase. Then, the ionic compounds are butylated with BuMgCl and the final organic solution is analyzed by GC-MS-SIM. The elimination of both foam and gels in the extraction step and the general procedure for the urine are discussed. The recovery of compounds ranges from 105.1% for Me3Pb+ to 97.2% for Et3Pb+ using hexane as extracting agent and detection limits are 18.4 pg/ml of Me3Pb+ and 19.2 pg/ml of Et3Pb+ in urine. The speciation of ionic alkylleads in the urine of a petrol station worker showed a value of 27.9 pg/ml of Me3Pb+ in urine and Et3Pb+ was below the detection limit.

Ethanol↗

Speciation of low molecular weight Al complexes in serum of CAPD patients.

Speciation of LMW--Al complexes was performed in human serum of six continuous ambulatory peritoneal dialysis (CAPD) patients in order to investigate the individual variability in the percentage and the composition of LMW--Al species. The total concentration of Al in serum ranged from 10 to 120 ng ml(-1). The samples with high total concentration of Al were analysed directly, while those of low total Al concentration were spiked with Al(3+). Spiked and non-spiked samples (100--120 ng ml(-1) of total Al) were microultrafiltered through a membrane filter (cut-off 30,000 Da) to separate Al-transferrin from LMW-Al complexes. On an anion-exchange fast protein liquid chromatography (FPLC) column, 0.2 ml of filtrate was injected. An aqueous -- 4 mol l(-1) NH(4)NO(3) linear gradient elution was applied for 10 min to separate LMW--Al complexes. Fractions of 0.2 ml collected throughout the chromatographic run were diluted 1:1 with water and Al determined 'off line' by electrothermal atomic absorption spectrometry (ETAAS). The characterisation of LMW-Al species eluted under the chromatographic peaks was performed also by electrospray tandem mass spectrometric (ES-MS-MS) analysis. It was found experimentally that the percentage of LMW--Al species in spiked and non-spiked serum ranged from 25 to 50% (in one non-spiked sample 100%). The following LMW--Al species were separated and identified during the chromatographic run: Al-phosphate and a mixture of Al-citrate and ternary Al-citrate--phosphate complexes. It was found experimentally that the distribution of these species varied among particular patients. Similar distribution of LMW--Al species was found in spiked serum of healthy volunteers.

Aluminum Compounds↗

The Bathyclarias-Clarias species flock. A new model to understand rapid speciation in African great lakes.

Phylogenetic relationships between seven species of the catfish species flock from Lake Malawi (genus Bathyclarias) and other Clariid catfish have been investigated using cytochrome b partial sequences. Here we demonstrate that this species flock originated from a widespread, generalist species, Clarias gariepinus, still occurring in the lake. Bathyclarias species and their ancestor C. gariepinus form a simple model that can be used to understand the mechanisms of adaptation and rapid speciation in African Great lakes.

Adaptation, Physiological↗

Cryptic speciation suspected by morphometry within Lutzomyia runoides.

Clear-cut variation in the length of genital filaments amongst Bolivian specimens of Lutzomyia runoides (Fairchild & Hertig, 1953), of the species group aragaoi, allowed us to recognise two different, non-overlapping populations living in sympatry. The additional observation of their mutually exclusive colonisation of isolated trees strongly suggested the existence of cryptic speciation. Multivariate, size-in and size-free analyses bearing on characters other than genital filaments could separate the two putative cryptic species of L. runoides, and showed that they were different from L. inflata, previously regarded as conspecific.

Analysis of Variance↗

Arsenic speciation in human urine reference materials using high-performance liquid chromatography with inductively coupled plasma mass spectrometric detection.

Six arsenic compounds including arsenocholine, arsenobetaine, dimethylarsinic acid, methylarsonic acid, arsenous acid and arsenic acid were separated by high-performance liquid chromatography (HPLC) on a Hamilton PRP-X100 anion-exchange column using isocratic elution and detected by inductively coupled plasma mass spectrometry (ICP-MS). This analytical procedure was applied to the speciation of arsenic compounds in human urine. The influence of urine matrix on the separation of arsenic compounds was evaluated and the determination of arsenic compounds was not hampered by the ArCl interference which has often been encountered in ICP-MS. Three human urine reference materials, SRM 2670 normal level, SRM 2670 elevated level and Lyphocheck urine metal control 1, were analyzed with respect to arsenic compounds by HPLC-ICP-MS. The results were found to be in good agreement with the certified total arsenic concentration in the reference materials. Six arsenic compounds were detected. Arsenobetaine was found to be present in all of the investigated human urine reference materials.

Arsenic↗

Mercury speciation in fluorescent lamps by thermal release analysis.

In this work, mercury speciation in phosphorus powder matrices and soda lime glass waste from new and spent fluorescent lamp wastes has been studied by thermo-desorption/atomic absorption spectrometry (TDAAS), X-ray diffraction (XRD), cold vapor-atomic absorption (CV-AAS) and atomic emission spectrometry/inductively coupled plasma (ICP/AES). TDAAS results show the presence of oxidized forms of mercury, i.e., Hg(1+) and Hg(2+), especially in wastes with high mercury concentration. Such forms are mobile, and therefore represent a potential hazard waste material. Glass TD profiles of spent fluorescent lamps suggested the presence of mercury strongly linked to the matrix, which desorbs only at high temperatures.

Hazardous Waste↗

Speciation. Down the bottleneck?

Experiments in which laboratory populations of fruitflies have been repeatedly passed through bottlenecks fail to support 'founder-effect' models of speciation.

Animals↗

Selfish operons and speciation by gene transfer.

Bacterial genes providing for single metabolic functions are found in operons, possibly because this organization allows efficient horizontal transfer among organisms. Transferred genes can confer novel metabolic phenotypes on their new hosts and allow rapid, effective exploitation of new environmental niches. Moreover, the mobility of selfish operons may facilitate bacterial speciation.

Bacteria↗

Chemical speciation used to assess [S,S']-ethylenediaminedisuccinic acid (EDDS) as a readily-biodegradable replacement for EDTA in radiochemical decontamination formulations.

Preliminary investigations into the replacement of widely used chelating agents for industrial cleansing of radionuclide contaminated items using readily biodegradable alternatives which have equivalent effectiveness, have been made using chemical speciation simulation programs and databases such as the JESS system. The chelation of radionuclide cations by [S,S']-EDDS has been compared with traditional decontamination agents, EDTA and citrate. Models indicate that in many respects, [S,S']-EDDS compares favourably with EDTA.

Americium↗

A new approach to monitoring trace element concentrations and speciation in wounds and wound fluids.

Combined application of potentiometric stripping analysis (PSA) and computer simulation of speciation analysis has been used to determine the total element concentrations and the proportions of the different chemical species of copper, manganese and zinc present in human would fluids. With samples of 0.5 to 1 cm3 the coefficient of variation lies in the range of 5-10%. In eight patients the concentrations of Cu and Zn were greater than those expected in blood plasma, but for Mn the observed concentrations lay with the range expected for plasma.

Cholecystectomy↗

Silver speciation during chronic toxicity tests with the mysid, Americamysis bahia.

A 28-day chronic toxicity test and two 7-day chronic estimation toxicity tests were conducted with silver nitrate (AgNO(3)) and the marine invertebrate, Americamysis bahia, in 20 per thousand (parts-per thousand) salinity seawater. One 7-day test was initiated with 7-day-old mysids and the second was initiated with <24-h-old mysids. There was very good agreement between the three toxicity tests. The no-observed-effect concentration (NOEC) values from the 28-day test, the 7-day test initiated with 7-day-old mysids, and the 7-day test initiated with <24-h-old mysids were 34, 65 and 38 microg/l silver, respectively. The 96-h LC50 values from the 28-day toxicity test and the 7-day toxicity test initiated with 7-day old mysids were 260 microg/l, and the 96-h LC50 value from the 7-day toxicity test initiated with <24-h-old mysids was 280 microg/l. Free ionic silver, Ag(+), concentrations measured with a silver electrode were in good agreement with concentrations calculated using total dissolved silver and chloride concentrations. Mean measured concentrations of Ag(+) in the test solutions ranged from 0.99 to 25 ng/l for the dissolved silver concentrations that ranged from 34 to 410 microg/l silver, indicating that free ionic silver varied from 0.003 to 0.006% of the silver dissolved in the 20 per thousand salinity seawater. Understanding the relationship of salinity and silver speciation, and the effect of this relationship on chronic invertebrate toxicity, will be useful for development of a marine biotic ligand model (BLM) and a water quality criterion for silver. This model could provide an important tool for improving the relationship of laboratory toxicity test results and predicted effects in natural environments, where variations in salinity may act to modify the toxicity of silver and other metals.

Animals↗

Morphological variability in the malaria vector, Anopheles moucheti, is not indicative of speciation: evidences from sympatric south Cameroon populations.

Anopheles moucheti is a major human malaria vector in the vicinity of slow moving rivers in the tropical forests of Central Africa. Morphological variations in natural populations of A. moucheti led to the designation of three morphological forms named A. moucheti moucheti, A. moucheti nigeriensis and A. moucheti bervoetsi. Using allozyme markers, we investigated to which extent morphological and/or geographical populations of A. moucheti were genetically differentiated. Mosquitoes were collected from four villages 20-200 km distant apart in south Cameroon, where specimens from each morphological form were found in sympatry. All populations appeared highly homogenous across both morphological type and geographic location. Significant genetic differentiation was only observed between two locations 150 km apart (F(st)=0.029; P=0.006), while no pairwise F(st) estimate between morphological forms reached statistical significance. Further evidence against any taxonomic value of this morphological classification was provided by direct observation of morphological variation within the progeny of field-collected females from all three types. Single female offspring always belonged to at least two morphologically recognised types and most often, a mixture of all three forms was observed. Our results therefore demonstrate that morphological variability within A. moucheti natural populations is not indicative of speciation. With this respect, restricted migration of individuals across river systems may be a more important factor in shaping population genetic structure of A. moucheti.

Animals↗

Parity between kinetoplast DNA and mini-exon gene sequences supports either clonal evolution or speciation in Trypanosoma rangeli strains isolated from Rhodnius colombiensis, R. pallescens and R. prolixus in Colombia.

Trypanosoma rangeli are kinetoplastid protozoa which have been largely recognized and defined in several Latin American countries in relation to T. cruzi, because the two trypanosome species are frequently found in mixed infections in triatominae vectors, humans and a variety of wild and domestic mammals. We report the molecular characterization of 18 T. rangeli strains isolated from the salivary glands of naturally infected Rhodnius colombiensis, R. pallescens and R. prolixus by using two independent set of molecular markers. kDNA and mini-exon amplification indicated dimorphism within both DNA sequences: KP1, KP2 and KP3 or KP2 and KP3 products for kDNA mini-circles and 380 or 340bp products for the mini-exon. One of two associations was observed within individual strains: KP1, KP2 and KP3 kDNA products with the 340bp mini-exon product and the KP2 and KP3 kDNA products with the 380bp mini-exon product. Independent mitochondrial and nuclear molecular markers showed a clear division of T. rangeli into two major phylogenetic groups associated with specific vectors in Colombia and in other Latin America countries. These results support either clonal evolution or speciation in T. rangeli populations, probably derived as a secondary adaptation to their parasitic condition in triatomine vectors.

Animals↗

Mapping and characterization of a 'speciation gene' in Drosophila.

Almost nothing is known about the identity of the genes causing reproductive isolation between species. As a first step towards molecular isolation of a 'speciation gene', I mapped and partly characterized a gene causing hybrid male sterility in Drosophila. This analysis shows that sterility of D. melanogaster males who carry the 'dot' fourth chromosome from D. simulans is due entirely to a very small region of the D. simulans chromosome (including only about 5 salivary gland bands or approximately 250 kb of DNA). Thus the hybrid sterility effect of the D. simulans fourth chromosome is almost surely due to a single gene of very large effect (here named hms, hybrid male sterile). Hms is zygotically acting, and the D. simulans allele of hms is completely recessive. Furthermore, complementation tests suggest that hms is not an allele of any known locus in D. melanogaster.

Alleles↗