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Chemical and physical speciation of arsenic in a small pond receiving gold mine waste effluent.

The chemical and physical speciation of arsenic in a small pond that receives wastewater from a gold mine operation in western Victoria, Australia was studied using differential pulse polarography. By using different sample pretreatments, distinction between the physical states (dissolved or particulate As), between the oxidation states (As(III) or As(V)), and between the degrees of lability (labile or strongly bound) was achieved. The results are interpreted in terms of the physicochemical properties with reference to the use of the pond as a settlement dam for gold mining effluent. The speciation of arsenic was found to vary markedly with the physicochemical properties of the water. A model for the behavior of arsenic in the pond is proposed.

Animals↗

Elemental speciation studies--new directions for trace metal analysis.

Elemental speciation is reviewed as a new approach to trace metals analysis. The importance of metal speciation relative to total metal analysis is considered. Various types of chromatographic separation methods using inductively coupled plasma-mass spectrometry (ICP-MS) detection are discussed. A brief introduction to the instrumental techniques is given, as well a discussion of coupling the instrumentation. Various chromatographies are included with an emphasis on liquid chromatography (LC). Gas chromatography (GC) and capillary electrophoresis (CE) are also discussed. Application examples contrast and compare the advantages and disadvantages of ICP- MS with other detection methods. Summary tables are included for two of the LC methods.

Chromatography, Liquid↗

Dynamics of aluminum speciation in forest-well drainage waters from the Rhode River watershed, Maryland.

This paper reports an investigation of the dynamics of aluminum (Al) speciation in the forest-well waters from study site 110 of the Rhode River watershed, a representative sub-unit of Chesapeake Bay. Seasonal changes of Al speciation are evaluated by a modified MINEQL computer model using chemical equilibrium calculation. It was found that Al-F and Al-Org complexes were the dominate forms, whereas toxic forms of Al3+ and Al-OH were not significant. This indicates that Al toxicity is not very serious in the Rhode River area due to the high concentrations of fluoride and organic materials, even though sometimes pH is very low (approximately 4). Increased H+ or some other associated factors may be responsible for the decline in fish and amphibian population on the watershed.

Acid Rain↗

The systematic study of aluminium speciation in medium concentrated aqueous solutions.

Industrial applications and environmental problems involving the aqueous chemistry of aluminium require an understanding of the speciation of this metal ion at a wide range of concentrations. The formation of polynuclear species is of special interest due to the complexity of the hydrolysis mechanisms and the diversity of the hydrolysis products. Kinetic aspects of speciation are also important considering the different stability ranges of polycationic species formed during the hydrolysis process. In the present paper we report results of systematic studies on the formation of aluminium polycations at room temperature. Automated potentiometric titrations have been used to study the hydrolysis of aluminium-ions in solutions (0.01-0.2 M) on a short time scale (2 min between titrant additions). (27)Al NMR spectroscopy and dynamic light scattering have been used for investigations on a longer time scale (24 h). The effects of alkali strength (KOH, NH(4)OH and KHCO(3)) and concentration (0.45-2.0 M), counterion identity (Cl(-), NO(3)(-), SO(4)(2-)) and ionic strength have been investigated. Optimum conditions for the generation of Al(13)-mer are proposed on short and long time scales. On a short time scale, aluminium chloride and nitrate should be used as starting materials, KOH and KHCO(3) should be used for hydrolysis and experiments conducted at low ionic strength. For solutions that have been left to age, there is a considerable hydrolysis window that can be used to generate significant quantities of the Al(13)-mer that vary little with the alkali used. Al(13)-mer species are not generated from alum as the precursor. The presence of sulphate ions alters the pathway of aluminium polymerisation to form polymeric and solid materials. On the basis of the potentiometric titration data, dynamic light scattering and (27)Al NMR measurements evidence is provided for the detrimental role of sulphate-ions in the formation of Al(13)-mer and an alternative mechanism of aluminium ion polycondensation is proposed, based on the increased stability of monomeric and oligomeric species (dimer and trimer) in the presence of sulphate-ions.

Alkalies↗

Vanadium(IV/V) speciation of pyridine-2,6-dicarboxylic acid and 4-hydroxy-pyridine-2,6-dicarboxylic acid complexes: potentiometry, EPR spectroscopy and comparison across oxidation states.

Evaluation of stability of vanadium(IV) and (V) complexes under similar conditions is critical for the interpretation and assessment of bioactivity of various vanadium species. Detailed understanding of the chemical properties of these complexes is necessary to explain differences observed their activity in biological systems. These studies are carried out to link the chemistry of both vanadium(IV) and (V) complexes of two ligands, 2,6-pyridinedicarboxylic acid (dipicolinic acid, H(2)dipic) and 4-hydroxy-2,6-pyridinedicarboxylic acid (H(2)dipic-OH). Solution speciation of the two 2,6-pyridinedicarboxylic acids with vanadium(IV) and vanadium(V) ions was determined by pH-potentiometry at I=0.2 M (KCl) ionic strength and at T=298 K. The stability and the metal affinities of the ligands were compared. Vanadium(V) complexes were found to form only tridentate coordinated 1:1 complexes, while vanadium(IV) formed complexes with both 1:1 and 1:2 stoichiometries. The formation constant reflects hindered coordination of a second ligand molecule, presumably because of the relatively small size of the metal ion. The most probable binding mode of the complexes was further explored using ambient and low temperature EPR spectroscopy for vanadium(IV) and 51V NMR spectroscopy for vanadium(V) systems. Upon complex formation the pyridinol-OH in position 4 deprotonates with pK approximately 3.7-4.1, which is approximately 6 orders of magnitude lower than that of the free ligand. The deprotonation enhances the ligand metal ion affinity compared to the parent ligand dipicolinic acid. In the light of the speciation and stability data of the metal complexes, the efficiency of the two ligands in transporting the metal ion in the two different oxidation states are assessed and discussed.

Electron Spin Resonance Spectroscopy↗

Speciation study of the anti-inflammatory drug tenoxicam (Htenox) with Cu(II): X-ray crystal structure of [Cu(tenox)(2)(py)(2)].EtOH.

A speciation study was carried out in aqueous solution of the anti-inflammatory drug tenoxicam (Htenox), under quasi-physiological conditions (temperature of 37 degrees C and ionic strength 0.15 M NaCl) in order to determine the acidity constants from spectrophotometric studies, the pK(a) values found being pK(1)=1.143+/-0.008 and pK(2)=4.970+/-0.004. Subsequently, the spectrophotometrical speciation of the different complexes of Cu(II) with the drug was performed under the same conditions of temperature and ionic strength, observing the formation of Cu(Htenox)(2)(2+) with log beta(212)=20.05+/-0.01, Cu(tenox)(2) with log beta(012)=13.6+/-0.1, Cu(Htenox)(2+) with log beta(111)=10.52+/-0.08, as well as Cu(tenox)(+) with log beta(011)=7.0+/-0.2, all of them in solution, and solid species Cu(tenox)(2)(s) with an estimated value of log beta(012)(s) approximately 18.7. The crystalline structure of the complex [Cu(tenox)(2)(py)(2)]. EtOH, was also determined, and it was observed that tenoxicam employs the oxygen of the amide group and the pyridyl nitrogen to bond to the cation.

Anti-Inflammatory Agents, Non-Steroidal↗

NMR studies of copper speciation in the bovine rumen environment.

Dietary copper supplements containing complexed copper have been asserted to be more bioavailable than 'inorganic' supplements. Since bioavailability is intimately related to the particular metal ion species that exist in any given environment, studies of solution speciation can be used to examine this assertion. In a previous study, our computer modeling of copper speciation in bovine saliva indicated that when a lysine-complexed copper supplement is used, the complex will not persist. In the present study, these conclusions are supplemented and extended using 1H NMR experiments. Lysine and the copper(II)-lysine system are characterized, and chemical shifts of the individual species obtained. Chemical shift values for the copper(II)-lysine-bovine saliva system can then be predicted. Results show good agreement with experimental values. The scope of the computer modeling is then expanded to include the major low molar mass ligands present in the rumen. Implications of the results are discussed. The validity of this rumen model is further evaluated by NMR investigations on biological samples. The study provides further evidence that complexes such as copper(II)-lysine would disintegrate in the gastrointestinal tract, and are unlikely to be absorbed intact.

Animal Feed↗

Chemical speciation applied to bio-inorganic chemistry.

The processes of converting new chemistry into new healthcare, environment-friendly, products are considerably facilitated when chemical speciation data are available. These identify causal links between speciation and biological responses based upon specific chemical species rather than total concentrations. The effective roles of bismuth for ulcer treatment, of Ca, Zn, Sn and F in dentifrices, and of zinc species and common cold symptoms are described. A new readily biodegradable ligand for minimising the environmental impact of washing powders, Al and Alzheimer's disease (and the absence of a causal link), and an audit of Cu and Zn flow from wound dressing through wound fluid to healing tissue, are all discussed in detail.

Aluminum↗

Kinetics of radiolabelled silver uptake and depuration in the gills of rainbow trout (Oncorhynchus mykiss) and European eel (Anguilla anguilla): the influence of silver speciation.

We examined the influence of speciation on the kinetics of silver uptake and depuration in the gills of two freshwater fish, the rainbow trout (Oncorhynchus mykiss) which has high branchial Na(+) and Cl(-) uptake rates and is relatively sensitive to silver, and the European eel (Anguilla anguilla, yellow stage) which has low ion uptake rates and is relatively resistant to silver. Fish previously acclimated to the appropriate chloride level were exposed to 110mAgNO(3) (1.3 microg l(-1), sublethal) for 24 h in synthetic softwater with either low (10 microM) or high (1200 microM) chloride concentration, and then followed over a subsequent 67-day post-exposure period in silver-free water of the same chloride content. The exposures were therefore mainly to the free ion, Ag(+) in the low chloride water versus mainly to the neutral aqueous complex, AgCl(aq) in the high chloride water. In trout, but not in eel, water chloride is known to protect against physiological disturbances and toxicity caused by Ag(+). In both fish species, at both chloride levels, silver uptake exhibited complex kinetics. Gill silver loading occurred slowly until 6 h, then rose greatly to a peak at 12 h, followed by significant net depuration thereafter during continued exposure. By 24 h, net gill loading was three- to fivefold greater from AgCl(aq) than from Ag(+) exposure in both species, and threefold greater in trout than in eel under both conditions, with trout holding a lower fraction of the whole body burden in their gills. During the post-exposure period, depuration of silver from the gills occurred rapidly in trout, but very slowly in eel, such that gill silver burdens were greater in eel throughout the 67-day period on both an absolute and relative basis (e.g. 35% of whole body burden in eel versus <3% in trout at day 8). The kinetics of depuration were described by two phase exponential models, with break points between the fast and slow phases at 1 and 15 days for trout and eel, respectively. We conclude that speciation affects not only uptake rates but also the kinetics of depuration. When silver is loaded from AgCl(aq) it is clearly more labile than from Ag(+) exposures, with 1.6-1.8-fold greater loss rates during the fast phases in both species. Differences in branchial silver uptake between eel and trout correlate well with differences in acute toxicity, but are not as large as differences in ion uptake rates. The complex time-dependent patterns of gill loading, and the higher loading from AgCl(aq) than from Ag(+), mean that gill total silver burden is not an appropriate endpoint for biotic ligand modelling.

Adaptation, Physiological↗

Sexual selection and speciation.

The power of sexual selection to drive changes in mate recognition traits gives it the potential to be a potent force in speciation. Much of the evidence to support this possibility comes from comparative studies that examine differences in the number of species between clades that apparently differ in the intensity of sexual selection. We argue that more detailed studies are needed, examining extinction rates and other sources of variation in species richness. Typically, investigations of extant natural populations have been too indirect to convincingly conclude speciation by sexual selection. Recent empirical work, however, is beginning to take a more direct approach and rule out confounding variables.

Journal Article↗

Phylogenetics and speciation.

Species-level phylogenies derived from molecular data provide an indirect record of the speciation events that have led to extant species. This offers enormous potential for investigating the general causes and rates of speciation within clades. To make the most of this potential, we should ideally sample all the species in a higher group, such as a genus, ensure that those species reflect evolutionary entities within the group, and rule out the effects of other processes, such as extinction, as explanations for observed patterns. We discuss recent practical and theoretical advances in this area and outline how future work should benefit from incorporating data from genealogical and phylogeographical scales.

Journal Article↗

Chromosomal rearrangements and speciation.

Several authors have proposed that speciation frequently occurs when a population becomes fixed for one or more chromosomal rearrangements that reduce fitness when they are heterozygous. This hypothesis has little theoretical support because mutations that cause a large reduction in fitness can be fixed through drift only in small, inbred populations. Moreover, the effects of chromosomal rearrangements on fitness are unpredictable and vary significantly between plants and animals. I argue that rearrangements reduce gene flow more by suppressing recombination and extending the effects of linked isolation genes than by reducing fitness. This unorthodox perspective has significant implications for speciation models and for the outcomes of contact between neospecies and their progenitor(s).

Journal Article↗

Transfer of radioactivity to fruit: significant radionuclides and speciation.

One of the roles of the BIOMASS Theme 3 Fruit Working Group was to identify significant radionuclides to support its work programme. This paper provides a short review of radionuclide emissions to atmosphere together with comments on their relative dosimetric impacts to identify those radionuclides most relevant to the Fruit Working Group. Speciation of the identified radionuclides is also discussed to identify the most likely chemical forms to which fruits might be exposed. It is noted that no information currently exists on radionuclide speciation in regard to the uptake and retention of radionuclides in fruit crops.

Air Pollutants, Radioactive↗

Runoff rates, chemical speciation and bioavailability of copper released from naturally patinated copper.

The release of copper, induced by atmospheric corrosion, from naturally patinated copper of varying age (0 and 30 years) has been investigated together with its potential ecotoxic effect. Results were generated in an interdisciplinary research effort in which corrosion science and ecotoxicology aspects were combined. The aim of the investigation was to elucidate the situation when copper-containing rainwater leaves a roof in terms of runoff rate, chemical speciation, bioavailability and ecotoxicity effects. Data have been collected during a three-year field exposure conducted in the urban environment of Stockholm, Sweden. The potential environmental effects have been evaluated using a combination of a copper specific biosensor test with the bacterium Alcaligenes eutrophus and the conventional 72-h growth inhibition test with the green alga Raphidocelis subcapitata. The results show annual runoff rates between 1.0 and 1.5 g/m2 year for naturally patinated copper of varying age. The runoff rate increased slightly with patina age, which mainly is attributed to the enhanced first flush effect observed on thicker patina layers. The total copper concentration in investigated runoff samplings ranged from 0.9 to 9.7 mg/l. Both computer modeling and experimental studies revealed that the majority (60-100%) of released copper was present as the free hydrated cupric ion, Cu(H2O)6(2+), the most bioavailable copper species. However, other copper species in the runoff water, such as, e.g. Cu(OH)+ and Cu2(OH)2(2+), were also bioavailable. The copper-containing runoff water, sampled directly after release from the roof, caused significant reduction in growth rate of the green alga. It should be emphasized that the results describe the runoff situation immediately after release from the copper roof and not the real environmental ecotoxicity. Therefore the data should only be used as an initial assessment of the potential environmental effect of copper runoff from building applications. Future risk assessments should also consider dilution effects of copper, changes in its chemical speciation and bioavailability during environmental entry, and type and sensitivity of the receiving ecosystem.

Biological Availability↗

Solid phase speciation of arsenic by sequential extraction in standard reference materials and industrially contaminated soil samples.

Availability, mobility, (phyto)toxicity and potential risk of contaminants is strongly affected by the manner of appearance of elements, the so-called speciation. Operational fractionation methods like sequential extractions have been applied for a long time to determine the solid phase speciation of heavy metals since direct determination of specific chemical compounds can not always be easily achieved. The three-step sequential extraction scheme recommended by the BCR and two extraction schemes based on the phosphorus-like protocol proposed by Manful (1992, Occurrence and Ecochemical Behaviours of Arsenic in a Goldsmelter Impacted Area in Ghana, PhD dissertation, at the RUG) were applied to four standard reference materials (SRM) and to a batch of samples from industrially contaminated sites, heavily contaminated with arsenic and heavy metals. The SRM 2710 (Montana soil) was found to be the most useful reference material for metal (Mn, Cu, Zn, As, Cd and Pb) fractionation using the BCR sequential extraction procedure. Two sequential extraction schemes were developed and compared for arsenic with the aim to establish a better fractionation and recovery rate than the BCR-scheme for this element in the SRM samples. The major part of arsenic was released from the heavily contaminated samples after NaOH-extraction. Inferior extraction variability and recovery in the heavily contaminated samples compared to SRMs could be mainly contributed to subsample heterogeneity.

Arsenic↗

Measured summertime concentrations of particulate components, Hg0, and speciated polycyclic aromatic hydrocarbons at rural sites in New York State.

Daily PM2.5 samples, Hg0 and speciated polycyclic aromatic hydrocarbon (PAH) were simultaneously collected at Potsdam and Stockton site in NY during the summers of 2000 and 2001. Samples for determination of the mass concentration and chemical composition of the PM2.5 were obtained with a speciation network PM2.5 sampler. Chemical composition including trace elemental composition, water-soluble ions, and elemental carbon were analyzed. Elemental mercury and PAHs were sampled separately. Daily PM2.5 concentrations ranged from 0.47 to 53.7 microg m(-3) at the Potsdam site, and from 0.82 to 47.23 microg m(-3) at the Stockton site with large daily differences between the two sites. Potsdam consistently had lower mass values than Stockton. The greatest contributors to the PM2.5 mass (generally >0.1 microg/m(3)) were sulfate, nitrate, ammonium, and BC at both sites. Seventeen PAHs were identified at each site in 2000 and the average total concentrations were 3.2 ng/m(3) and 2.9 ng/m(3) at the Potsdam and Stockton sites, respectively. The mean vapor phase mercury concentration at the Potsdam site (2.4 +/-1.2 ng m(-3), n=93) was higher than that at the Stockton site (1.2 +/- 1.0 ng m(-3), n=60) in 2000, whereas in 2001, the average concentrations were 1.1 ng m(-3) and 1.6 ng m(-3) at the Potsdam and Stockton sites, respectively. In general, vapor phase mercury concentrations increased with increasing ambient temperature at the Stockton site in 2000. These differences in values between 2000 and 2001 can be largely explained by distinct differences in the meteorological regimes that dominated in the different years.

Aerosols↗

Trace metal speciation and bioavailability in urban soils.

Urban soils often contain concentrations of trace metals that exceed regulatory levels. However, the threat posed by trace metals to human health and the environment is thought to be dependent on their speciation in the soil solution rather than the total concentration. Three inactive railway yards in Montréal, Québec, were sampled to investigate the speciation and bioavailability of Cd, Cu, Ni, Pb and Zn. Soil solutions were obtained by centrifuging saturated soil pastes. In the soil solutions, up to 59% of the dissolved Cd was in its free ionic form. For Cu, Pb and Zn, organic complexes were the predominant species. Over 40% of Ni was present as inorganic complexes if the solution pH exceeded 8.1. Multiple regression analyses showed that pH and total metals in soil were significantly correlated with the activities of free metal ions, except for Cd(2+), which only had a weak correlation with soil pH. Free, dissolved and total soil metals were tested for their ability to predict metal uptake by plants in the field. However, none of these metal pools were satisfactory predictors. The results indicated that in these urban soils, trace metals were mainly in stable forms and bioavailability was extremely low.

Journal Article↗

Speciation of copper in the incineration fly ash of a municipal solid waste.

The speciation of copper and zinc in the incineration fly ash of a municipal solid waste in Taiwan was investigated in the present work. By the least-squares fitted X-ray absorption near edge structural (XANES) spectroscopy, we found that CuCO3, CuOH2, and CuO (fractions of 0.09, 0.39 and 0.51, respectively) were the main copper species in the fly ash. Quantitative analysis of the extended X-ray absorption fine structural (EXAFS) spectra indicated that the bond distance of Cu-O in the fly ash was 1.96 A with a coordination number (CN) of 3.9 in the first shell of copper. In the second shell, the bond distance and CN of Cu-(O)-Cu were 2.91 A and 2.7, respectively. In addition, speciation of Zn was also examined in the same X-ray absorption energy (8780-9970 eV). The bond distance of Zn-O and Zn-O-Zn were 1.97 and 2.94 A, respectively. However, the Zn-O-Cu structure was not found because of the physically unreasonable sigma(2) (Debye-Waller factor) values in the EXAFS data fitting process.

Air Pollutants↗