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PubMed2001

Properties of phylogenetic trees generated by Yule-type speciation models.

We investigate some discrete structural properties of evolutionary trees generated under simple null models of speciation, such as the Yule model. These models have been used as priors in Bayesian approaches to phylogenetic analysis, and also to test hypotheses concerning the speciation process. In this paper we describe new results for three properties of trees generated under such models. Firstly, for a rooted tree generated by the Yule model we describe the probability distribution on the depth (number of edges from the root) of the most recent common ancestor of a random subset of k species. Next we show that, for trees generated under the Yule model, the approximate position of the root can be estimated from the associated unrooted tree, even for trees with a large number of leaves. Finally, we analyse a biologically motivated extension of the Yule model and describe its distribution on tree shapes when speciation occurs in rapid bursts.

Animals↗

PubMed2003

Speciation of arsenic in human nail and hair from arsenic-affected area by HPLC-inductively coupled argon plasma mass spectrometry.

Nail and hair are rich in fibrous proteins, i.e., alpha-keratins that contain abundant cysteine residues (up to 22% in nail and 10-14% in hair). Although they are metabolically dead materials in the epidermis, the roots are highly influenced by the health status of the living beings and their analyses are used as a tool to monitor occupational and environmental exposure to toxic elements. The aims of the present study are to speciate arsenicals in human nail and hair and also to judge whether they should be used as a biomarker to arsenic (As) exposure and/or toxicity. All human fingernail and hair samples (n = 47) were collected from the As-affected area of West Bengal, India. Speciation of arsenicals in water extracts of fingernails and hair at 90 degrees C was carried out by HPLC-inductively coupled argon plasma mass spectrometer (ICP MS). Fingernails contained iAs(III) (58.6%), iAs(V) (21.5), MMA(V) (7.7), DMA(III) (9.2), and DMA(V) (3.0), and hair contained iAs(III) (60.9%), iAs(V) (33.2), MMA(V) (2.2), and DMA(V) (3.6). Fingernails contained DMA(III), but hair did not. The higher percentage of iAs(III) both in fingernails and hair than that of iAs(V) suggests more affinity of iAs(III) to keratin. Although all arsenicals in fingernails and hair correlate to As exposure positively, As speciation in fingernails seems to be more correlated with arsenism than that in hair. Exogenous contamination is a confounding factor for hair to consider it as a biomarker, whereas this is mostly absent in fingernails, which recommends it to be a better biomarker to arsenic exposure. DMA(III) content in fingernails and DMA(V) contents in both fingernails and hair could be the biomarker to As exposure.

Arsenic↗

PubMed2003

Effects of raw water conditions on solution-state aluminum speciation during coagulant dilution.

The speciation of aluminum in solutions of alum and various prehydrolyzed, aluminum-based water treatment coagulants was investigated by 27Al NMR at 5 degrees C and 25 degrees C. Alum solutions were seen to contain only mononuclear species including an AlSO4(+) complex, while the prehydrolyzed coagulant solutions contained polynuclear aluminum species, as well. The relative proportions of both polynuclear species and AlSO4(+) complex decreased in cold water. The presence of organic matter had little effect on the speciation of aluminum in diluted alum, but markedly reduced the relative proportion of the tridecamer species in the prehydrolyzed coagulant solutions. The relationship between Al speciation in the coagulants and organic matter removal during jar tests was considered, and the possible role of sulfate in both the formation of the tridecamer species and the effect of organic matter on coagulation efficiency was discussed.

Alum Compounds↗

PubMed2001

Speciation and mobility of cadmium in straw and wood combustion fly ash.

Two fly ashes from biomass combustion have been analysed regarding cadmium speciation and mobility. A fly ash from straw combustion contained 10 mg Cd/kg dry matter, and around 50% of the cadmium was leachable in water. The possible main speciation of cadmium in this fly ash was CdCl2. When adding this fly ash to agricultural soil a threat for groundwater contamination and plant uptake is existing. A fly ash from wood chip combustion had 28.6 mg Cd/kg dry matter. In this fly ash, the cadmium was bound more heavily, with only small amounts of cadmium leached in mild extractants. A possible speciation of cadmium in this fly ash was as oxide or as CdSiO3. Long-term effects and accumulation of cadmium could be a problem when adding this fly ash to agricultural or forest soils.

Agriculture↗

PubMed2002

Heavy metal content and speciation in groundwater of the Guadiamar river basin.

This work presents the conclusions of a speciation study concerning Zn, Cd, Pb and Cu in groundwater from ten wells in the alluvial aquifers of the Guadiamar river, affected by Aznalcollar mine tailing spill (April 1998). The sampling campaign took place in January 2000, almost two years after the mining accident. Four metal fractions were determined: labile metal forms, H+ exchangeable metal forms, strongly inert forms (associated with organic and inorganic matter in solution), and forms associated with suspended matter. Total metal concentration in groundwater followed the trend Cd < Pb < Cu < Zn. The speciation study showed that Zn and Cd were present to a great extent in available forms (labile and H+ exchangeable), while Pb and Cu were found mostly in the less available forms (strongly inert). These results can illustrate the potential value of the speciation tool for the follow-up of spill-induced pollution in the area.

Biological Availability↗

PubMed2002

Speciation of arsenic and chromium metal ions by reversed phase high performance liquid chromatography.

The speciation of arsenic [As(III) and As(V)] and chromium [Cr(III) and Cr(VI)] was carried out by high performance liquid chromatography. The column used was Econosil C18 (250 x 4.6 mm i.d., particle size 10 microm). The mobile phases consisted of water-acetonitrile (80:20, v/v) for arsenic and 10 mM ammonium acetate buffer (6.0 pH)-acetonitrile (10:90, v/v) for chromium speciation separately and respectively. The detection was carried out by UV-Vis at 410 nm and atomic absorption spectrometer (AAS) respectively and separately. The values of alpha and Rs of As(III) and As(V) species were 1.4 and 1.5 respectively while the values of alpha and Rs for Cr(III) and Cr(VI) were 1.35 and 0.2 respectively. The effect of the acetonitrile percentages was also carried out on the speciation of arsenic only. The relative standard deviation and limit of detection were in the range of 0.01-0.02 and 0.4-1.0 microg/ml respectively.

Acetonitriles↗

PubMed2003

Chemical speciation and extractability of Zn, Cu and Cd in two contrasting biosolids-amended clay soils.

An incubation experiment was conducted to study the chemical speciation and extractability of three heavy metals in two contrasting biosolids-amended clay soils. One was a paddy soil of pH 7.8 and the other was a red soil of pH 4.7 collected from a fallow field. Anaerobically digested biosolids were mixed with each of the two soils at three rates: 20, 40 and 60 g kg(-1) soil (DM basis), and unamended controls were also prepared. The biosolids-amended and control soils were incubated at 70% of water holding capacity at 25 degrees C for 50 days. Separate subsamples were extracted with three single extractants and a three-step sequential extraction procedure representing acetic acid (HOAc)-soluble, reducible and oxidisable fractions to investigate the extractability and speciation of the heavy metals. As would be expected, there were good relationships between biosolids application rate and metal concentrations in the biosolids-amended soils. The three heavy metals had different extractabilities and chemical speciation in the two biosolids-amended soils. Ethylene diamine tetraacetic acid extracted more Cu, Zn and Cd than did the other two single extractants. The oxidisable fraction was the major fraction for Cu in both biosolids-amended soils and the HOAc-soluble and reducible fractions accounted for most of the Zn. In contrast, Cd was present mainly in the reducible fraction. The results are discussed in relation to the mobility and bioavailability of the metals in polluted soils.

Acetates↗

PubMed2003

Horizontal and vertical variabilities of mercury concentration and speciation in sediments of the Gdansk Basin, Southern Baltic Sea.

The mercury compounds introduced to the environment because of anthropogenic activity are accumulated, mainly, in marine sediments. Both distribution of mercury in the Baltic Sea and factors affecting it are remain largely unknown. Due to its complex chemistry and variable conditions in the Baltic Sea bottom sediments, mercury may be reemitted to the overlaying water, and thus to the environment. The aim of this study was twofold. Total mercury contents were measured in sediments of the Gdansk Basin along a Vistula mouth (main source)--Gdansk Deep (deposition area) transect in order to assess spatial distribution of the element. Soft and sandy bottom sediment cores were collected and cut into slices. The mercury measurements consisted of acid digestion followed by CV-AAS determination. A five-step sequential extraction procedure involving measurements of mercury species water soluble, bound to humic substances and insoluble, was employed in order to investigate mercury speciation. On the basis of speciation results stability and remobilisation potential was assessed. The second aim was demonstrating that mercury gradients in vertical profiles of the investigated sediment cores exist. Total mercury contents varied in range from 28 ng/g x dw to 844 ng/g. Mercury associated with organic matter and sulphides, (respectively 39% and 49%) were the dominant species of the element. The results indicated that the river run-off is a source of mercury in the area. Vertical gradients of both total content and speciation of mercury in the soft sediments were attributed to both remobilisation from sediments, and decreasing trend in the anthropogenic load of the element deposited to sediments.

Baltic States↗

PubMed2002

Mercury speciation in the French seasonal snow cover.

Snow samples have been collected in the French Alps in 1998, 1999 and 2000 in order to measure both total Hg (HgT) and reactive Hg (HgR). Concentrations of HgT were between 13 and 130 pg g(-1) and HgR concentrations were below the detection limit (approximately 0.8 pg g(-1)). Hg speciation in snow was evaluated on the basis of ionic complexation equilibrium with chloride, hydroxide, oxalate. The pH of the snow was found to be an important parameter for Hg speciation. For pH values near 3, HgC2O4 is predominant in snow samples except for snow strongly influenced by anthropogenic sources (in which case HgCl2 predominates). When pH > 4, Hg(OH)2 and HgOHCl are predominant. These latter pH values are observed for precipitation not influenced by anthropogenic sources but more by soil erosion, e.g. Saharan dusts. The knowledge of Hgr speciation in snow is a key question for understanding the mechanisms of transformation of these complexes in snow after precipitation.

Journal Article↗

PubMed1999

Fungal production of citric and oxalic acid: importance in metal speciation, physiology and biogeochemical processes.

The production of organic acids by fungi has profound implications for metal speciation, physiology and biogeochemical cycles. Biosynthesis of oxalic acid from glucose occurs by hydrolysis of oxaloacetate to oxalate and acetate catalysed by cytosolic oxaloacetase, whereas on citric acid, oxalate production occurs by means of glyoxylate oxidation. Citric acid is an intermediate in the tricarboxylic acid cycle, with metals greatly influencing biosynthesis: growth limiting concentrations of Mn, Fe and Zn are important for high yields. The metal-complexing properties of these organic acids assist both essential metal and anionic (e.g. phosphate) nutrition of fungi, other microbes and plants, and determine metal speciation and mobility in the environment, including transfer between terrestrial and aquatic habitats, biocorrosion and weathering. Metal solubilization processes are also of potential for metal recovery and reclamation from contaminated solid wastes, soils and low-grade ores. Such 'heterotrophic leaching' can occur by several mechanisms but organic acids occupy a central position in the overall process, supplying both protons and a metal-complexing organic acid anion. Most simple metal oxalates [except those of alkali metals, Fe(III) and Al] are sparingly soluble and precipitate as crystalline or amorphous solids. Calcium oxalate is the most important manifestation of this in the environment and, in a variety of crystalline structures, is ubiquitously associated with free-living, plant symbiotic and pathogenic fungi. The main forms are the monohydrate (whewellite) and the dihydrate (weddelite) and their formation is of significance in biomineralization, since they affect nutritional heterogeneity in soil, especially Ca, P, K and Al cycling. The formation of insoluble toxic metal oxalates, e.g. of Cu, may confer tolerance and ensure survival in contaminated environments. In semi-arid environments, calcium oxalate formation is important in the formation and alteration of terrestrial subsurface limestones. Oxalate also plays an important role in lignocellulose degradation and plant pathogenesis, affecting activities of key enzymes and metal oxido-reduction reactions, therefore underpinning one of the most fundamental roles of fungi in carbon cycling in the natural environment. This review discusses the physiology and chemistry of citric and oxalic acid production in fungi, the intimate association of these acids and processes with metal speciation, physiology and mobility, and their importance and involvement in key fungal-mediated processes, including lignocellulose degradation, plant pathogenesis and metal biogeochemistry.

Biodegradation, Environmental↗

PubMed2001

Simulation of acid-base condition and copper speciation in the fish gill microenvironment.

pH, alkalinity, and mucus content in the fish gill microenvironment of carp (Cyprinus carpio) were measured by exposing fish to copper at various water pH levels using an apparatus which separates inspired and expired water. The relationship between pH levels inside and outside of the gill microenvironment, between pH and alkalinity, and between mucus secretion, pH, and copper exposure concentration were modeled. Copper speciation in the surrounding water and in the fish gill microenvironment was simulated using MINTEQA2 chemical equilibrium calculation software. The results of the modeling for pH, alkalinity, and mucus calculation were then adopted as inputs for purposes of parameter identification in the speciation modeling. The differences observed in the copper species distribution between that of the fish gill microenvironment and the surrounding water were based on the speciation modeling. The change in copper bioavailability for fish uptake was also examined. The results indicate the presence of an experimental pH balance point at 6.9, where the pH in the fish gill microenvironment is identical to that of the surrounding water. The observed deviation range in pH levels between that found at the gills and that of the surrounding water varied from -0.4 to 0.8 units. A sinusoidal model was developed for calculation of gill pH based on the pH of the surrounding water. Models calculating alkalinity either in the gill microenvironment or in the surrounding water and for estimating mucus secretion were also developed. The results of the chemical equilibrium calculations demonstrate that, within a pH range of 6-9, the dominant species of copper in bulk solution shifted from free ions to that of the hydroxo complex. With respect to the fish gill microenvironment, the dominant species found under acidic conditions were the mucus copper complex and free ions. Because of the influence of mucus complexation and pH change, bioavailable copper species in the fish gill microenvironment were significantly lower than that in the bulk solution, especially under acidic conditions.

Acid-Base Equilibrium↗

PubMedDate not supplied

Cadmium speciation and transport in the blood of the bivalve Mytilus edulis.

Cadmium (Cd) speciation in the blood plasma of Mytilus edulis was investigated using the metal speciation model MINTEQA2. In the presence of inorganic ions alone, Cd-chloro complexes dominated the speciation (97% of total Cd), with 3% as Cd2+. Inclusion of a novel Cd-binding histidine-rich glycoprotein (HRG) purified from mussel blood plasma decreased the contribution of chloro-complexes to 11.9%, with 86.8% of the Cd bound to the HRG and 1.3% present as Cd2+. Cd transfer from the blood plasma to the kidneys in vivo was studied by injecting 109Cd (both with and without additional chelation) into mussels. Oxine and EDTA complexed a significant amount of blood-borne Cd (23.7% Cd Oxine; 57.1% CdEDTA). In the presence of each chelator, plasma retained significantly more Cd, although there was no significant difference in Cd uptake by tissues (kidney, gill-mantle, and remaining viscera).

Animals↗

PubMed2000

Analysis and chemical speciation of copper and zinc in wound fluid.

A novel method for the analysis of trace element chemical speciation at parts per billion (ppb) levels in wound fluid samples both contributes to the fundamental inorganic biochemistry of the healing process and permits improved treatments. Potentiometric Stripping Analysis in combination with acid digestion has been used to quantify the total copper and zinc levels in a series of 0.5 ml samples of fluid obtained from surgical wounds. Further, the degree of blood contamination has been investigated using visible spectroscopy. The prevailing chemical speciation (chemical forms) of these total concentrations of copper and zinc amongst low molecular mass ligands in wound fluid has been investigated by computer modelling using JESS, the Joint Expert Speciation System. The model, involving 38 components, generates in the region of 3500 individual low molecular mass complexes including copper, zinc, iron, calcium and manganese species, and predicts that the majority of low molecular mass (lmm) copper complexes are electrically net-neutral, whilst those of zinc are predominantly charged. Further studies indicate that supplementing the concentrations of histidine and tryptophan may increase the net-neutral zinc fraction, the optimum effect being achieved at pH=7.4. This may be important in transporting zinc into healing cells.

Body Fluids↗

PubMed2001

Computer simulation of the distribution of aluminum speciation in soil solutions in equilibrium with the mineral phase imogolite.

The speciation of aluminum (Al) is a critical issue when evaluating the environmental and biological significance of elevated Al concentrations in soil solutions caused by acidic precipitation. Numerous studies have revealed that, with increased concentrations of silica acid in soil, the activity of Al species in soil solutions is greatly modified by SiO(4)(2-). However, thus far there has been little thorough theoretical modeling of this subject. This paper reports a computer simulation of the distribution of Al speciation in soil solutions in equilibrium with the mineral phase imogolite based on a chemical equilibrium calculation. The unique characteristic associated with imogolite reported by previous researchers can be explained theoretically by the proposed model. The dissolved silica has a remarkable influence on Al speciation: increasing concentrations of silica acid may effectively inhibit the formation of polymeric alumino-hydroxo species, and, furthermore, detoxify Al toxicity to plants.

Aluminum↗

PubMed2001

Histidine--rich glycoprotein in the blood of the bivalve Mytilus edulis: role in cadmium speciation and cadmium transfer to the kidney.

Cadmium transfer from M. edulis L. blood plasma to tissues was investigated in relation to its chemical speciation in the blood. 109Cd was injected into the posterior adductor muscle along with synthetic chelators oxine, ethylenediaminetetraacetic acid (EDTA) or cyclohexanediaminetetraacetic acid (CDTA). Chelator concentrations were chosen to bind up from 0 to 98.7% of the total blood Cd, based on speciation calculations using the geochemical speciation model MINTEQA2. Increases in synthetically chelated Cd were accompanied by linear decreases in the calculated percentages of Histidine-rich Glycoprotein (HRG)-bound Cd, and nonlinear decreases in Cd(2+) and Cd chloro-complexes. Cadmium uptake by the kidneys decreased with increasing percentage synthetic chelation, while uptake by other tissues was not affected by chelation. Results indicate that there is at least one mechanism of Cd uptake common to all M. edulis tissues, and an additional, more rapid uptake mechanism in the kidneys that is mediated by CdHRG.

Animals↗

PubMed2001

Genome duplication, divergent resolution and speciation.

What are the evolutionary consequences of gene duplication? One answer is speciation, according to a model initially called Reciprocal Silencing and recently expanded and renamed Divergent Resolution. This model shows how the loss of different copies of a duplicated gene in allopatric populations (divergent resolution) can promote speciation by genetically isolating these populations should they become reunited. Genome duplication events produce thousands of duplicated genes. Therefore, lineages with a history of genome duplication might have been especially prone to speciation via divergent resolution.

Animals↗

PubMed2000

Bimodal hybrid zones and speciation.

Contact zones exemplify a series of stages in speciation. In unimodal hybrid zones intermediates predominate; in bimodal zones hybrids are rare and parental forms predominate; and finally, species might overlap, but never hybridize. Recent studies show bimodality to be associated strongly with assortative mating or fertilization, and only weakly with overall levels of genetic divergence or intrinsic genomic incompatibility. Ecological divergence across most bimodal hybrid zones suggests that ecology contributes more to speciation than genomic incompatibility. This continuum of stable contact zones provides empirical evidence for a route to speciation, which does not require allopatry.

Journal Article↗

PubMed2001

Chronic speciation in periodical cicadas.

Allochronic speciation and reproductive character displacement are two intuitively attractive models of speciation. The first proposes that changes in the timing of life cycles produce new species, whereas the second suggests that speciation is due to the exaggeration of sexual isolation in sympatric populations. Clear examples of either process in nature remain elusive, despite some extensive searches. Two recent studies of mtDNA markers and behaviour of periodical cicadas in North America have identified a new species of cicada that seems to provide good evidence for the involvement of both processes in its origin.

Journal Article↗