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PubMed2004

Chemical speciation and phytoavailability of Zn, Cu, Ni and Cd in soil amended with fly ash-stabilized sewage sludge.

A sequential extraction method was used to determine chemical forms of Cu, Zn, Ni and Cd in fly ash-stabilized sludge. A loamy acid soil amended with fly ash-stabilized sludge was used to grow corn under greenhouse conditions. Sewage sludge amended with coal fly ash can reduce the availability of Cu, Zn, Ni and Cd in the sludge. Increasing fly ash amendment rate significantly reduced DTPA-extractable Cu, Zn, Ni and Cd concentrations. Percentages of Cu, Zn and Ni in residual fraction increased with an increase in fly ash amendment rates. Majority of Cu was associated with organic form, but Zn and Ni were associated with Fe-Mn oxide and residual forms. Addition of ash-amended sludge to soil significantly increased dry mass of corn. With coal fly ash amendment rate increasing, concentrations of Zn and Cu in shoot tissues of corn decreased significantly, but concentrations of Cd and Ni did not change significantly. Significant correlations were found between concentrations of Cu and Zn in corn shoot and oxide and total Cu fractions, and all chemical fractions of Zn in fly ash-stabilized sludge, respectively. Hence, ash amendment significantly reduced the availability of heavy metals by chemical modification of their chemical speciation into less available forms.

Biodegradation, Environmental↗
PubMed2000

Speciation in the vanadate-alanylhistidine-peroxide system.

The speciation in the quaternary aqueous H+-H2VO4(-)-H2O2-L-alpha-alanyl-L-histidine (Ah) system has been determined from quantitative 51V NMR measurements and potentiometric data (glass electrode). The study was performed in 0.150 M Na(Cl) medium at 25 degrees C. Data were evaluated with the computer program LAKE, which is able to treat combined potentiometric and NMR data. In the ternary H+-H2VO4(-)-Ah system, two complexes, (H+)p(H2VO4-)q(Ah)r, having (p, q, r) values (0, 1, 1) and (1, 1, 1) (pKa = 6.88) explain all data. In the quaternary H+-H2VO4(-)-H2O2-Ah system, seven complexes were determined in addition to all binary and ternary complexes, four with a V/X/Ah ratio 1:1:1 and three with a ratio 1:2:1 (X = peroxo ligand). VX2Ah2- and VX2Ah- (pKa = 8.26) are the main quaternary complexes and predominate in the pH range 5 to 9. Chemical shifts, compositions and formation constants for all the quaternary complexes are given, and equilibrium conditions are illustrated in distribution diagrams.

Alanine↗
PubMed2000

Aluminum speciation studies in biological fluids. Part 6. Quantitative investigation of aluminum(III)-tartrate complex equilibria and their potential implications for aluminum metabolism and toxicity.

Recent epidemiological studies have confirmed the existence of a correlation between aluminum level in low-silica drinking water and prevalence of Alzheimer's disease. Also, oral aluminum-based phosphate binders and antacids may induce acute aluminum toxicity. Whatever the source of the metal ingested, its bioavailability is a function of the chemical forms under which it occurs in the gastrointestinal tract, i.e. of the ligands with which the Al3+ ion may associate. Dietary acids in particular can favor the bioavailability of aluminum in different ways: by increasing its solubility, by complexing it into neutral species, and/or by acting indirectly on its absorption process. Among these, tartaric acid is commonly found in fruits and in industrial foods and drinks, and may therefore be ingested together with environmental or/and therapeutic aluminum. The present work examines its potential influence on aluminum bioavailability. Firstly, Al(III)-tartrate complex formation constants have been determined under physiological conditions (37 degrees C, 0.15 M NaCl). Then these constants have been used to simulate the influence of tartrate on aluminum speciation in different gastrointestinal situations in which phosphate was also taken into account. Under normal conditions of aluminum contamination, tartrate is expected to keep the metal soluble throughout the whole pH range of the small intestine, which is likely to enhance its bioavailability. Even at low concentrations, tartrate also gives rise to two neutral complexes that span over the 1.5-7.5 pH interval, a phenomenon that is aggravated by increased aluminum levels as may result from aluminum hydroxide therapy. The co-occurrence of dietary phosphate reduces the fraction of aluminum neutralized by tartrate under normal conditions, but this effect quickly decreases with increasing aluminum doses. Even the therapeutic use of aluminum phosphate is not expected to be totally safe in the presence of tartaric acid. As plasma simulations show that no aluminum mobilization can be expected from tartrate that could enhance aluminum excretion, avoiding ingestion of tartaric acid during any form of aluminum-based therapy appears advisable.

Aluminum↗
PubMed2001

CD spectroscopic study on the speciation and solution structure of copper(II) complexes of some tripeptides in combination with potentiometric and spectrophotometric results.

The combination of potentiometric, spectrophotometric and CD spectroscopic studies under the same conditions is expected to yield more reliable thermodynamic and structural information for a certain system. The matrix rank analysis of both the spectrophotometric and CD spectra series gives the necessary number of species to be taken into account in the calculations. Based on such speciation diagrams the molar spectra for individual complexes in the copper(II) Gly-Gly-Ala, Gly-Ala-Gly, Ala-Gly-Gly and Ala-Ala-Ala systems were obtained. The results allowed us to assign these spectra to two types of coordination species with the compositions CuLH(-1) and [CuLH(-2)](-). The sign and the intensity of the CD spectra are well related to the chirality and distance of the chiral center(s) in the ligand from the metal ion chromophore and the stability of the metal complexes. They are further on additive within the experimental error in both cases with respect to chiral centers: the sum of the CD spectra of the Gly-Gly-Ala, Gly-Ala-Gly and Ala-Gly-Gly complexes equals those of Ala-Ala-Ala complexes. The CD spectra strongly support the coordination also of the C-terminal part of the peptide in the CuLH(-1) complex of GGA, and even the deprotonation of the Ala peptide group instead of that belonging to Gly cannot be excluded.

Circular Dichroism↗
PubMed2001

Aluminum speciation studies in biological fluids. Part 7. A quantitative investigation of aluminum(III)-malate complex equilibria and their potential implications for aluminum metabolism and toxicity.

As a nonessential element, aluminum may be toxic at both environmental and therapeutic levels, depending on ligand interactions. Dietary acids that normally occur in fruits and vegetables and commonly serve as taste enhancers are good ligands of the Al(3+) ion. Malic acid is one of these and also one of the most predominant in food and beverages. The present paper reports an examination of its potential influence on aluminum bioavailability through speciation calculations based on Al(III)-malate complex formation constants especially determined for physiological conditions. According to the results obtained, malate appears to be extremely effective in maintaining Al(OH)(3) soluble over the whole pH range of the small intestine under normal dietary conditions. In addition, two neutral Al(III)--malate complexes are formed whose percentages are maximum from very low malate levels. When aluminum is administered therapeutically as its trihydroxide, the amount of metal neutralized by malate peaks as its solubility pH range regresses to its original limits in the absence of malate. The enhancing effect of malate towards aluminum absorption is therefore virtually independent of the aluminum level in the gastrointestinal tract. The presence of phosphate in the gastrointestinal juice is expected to limit the potential influence of malate on aluminum absorption. Under normal dietary conditions, phosphate effectively reduces the fraction of aluminum neutralized by malate but without nullifying it. Aluminum phosphate is predicted to precipitate when aluminum levels are raised as with the administration of aluminum hydroxide, but a significant amount of neutral aluminum malate still remains in solution. Even therapeutic aluminum phosphate is not totally safe in the presence of malate, even at low malate concentrations. As plasma simulations predict that no compensatory effect in favor of aluminum excretion may be expected from malate, simultaneous ingestion of malic acid with any therapeutic aluminum salt should preferably be avoided.

Aluminum↗
PubMed2003

Systematic studies on pH-dependent transformations of dinuclear vanadium(V)-citrate complexes in aqueous solutions. A perspective relevance to aqueous vanadium(V)-citrate speciation.

Vanadium(V) involvement in interactions with physiological ligands in biological media prompted us to delve into the systematic pH-dependent synthesis, spectroscopic characterization, and perusal of chemical properties of arising aqueous vanadium(V)-citrate species in the requisite system. To this end, facile reactions led to dinuclear complexes (NH(4))(4)[V(2)O(4)(C(6)H(5)O(7))(2)].4H(2)O (1) and (NH(4))(6)[V(2)O(4)(C(6)H(4)O(7))(2)].6H(2)O (2). Complex 1 and 2 were characterized by elemental analysis, FT-IR and X-ray crystallography. Complex 1 crystallizes in the monoclinic space group C2/c with a=16.998(5) A, b=16.768(5) A, c=9.546(3) A, beta=105.22(1) degrees, V=2625(1) A(3), and Z=4. Complex 2 crystallizes in the triclinic space group P1;, with a=9.795(4) A, b=9.942(4) A, c=9.126(3) A, alpha=90.32(1) degrees, beta=111.69(1) degrees, gamma=108.67(1) degrees, V=774.5(5) A(3), and Z=1. The structures of 1 and 2 were consistent with the presence of a V(V)(2)O(2) core, to which citrate ligands of differing protonation state were bound in a coordination mode consistent with past observations. Ultimately, the aqueous pH dependent transformations of a series of three dinuclear complexes, 1, 2 and (NH(4))(2)[V(2)O(4)(C(6)H(6)O(7))(2)].2H(2)O (3), all isolated at pH values from 3 to 7.5, were explored and revealed an important interconnection among all species. Collectively, pH emerged as a determining factor of structural attributes in all three complexes, with the adjoining acid-base chemistry unfolding around the stable V(V)(2)O(2) core. The results point to the participation of all three species in aqueous vanadium(V)-citrate speciation, and may relate the site-specific protonations-deprotonations on the dinuclear complexes to potential biological processes involving vanadium(V) and physiological ligand targets.

Citrates↗
PubMed2003

Chemical speciation of insulinomimetic VO(IV) complexes of pyridine-N-oxide derivatives: binary and ternary systems.

In order to estimate the impact of the low-molecular-mass (l.m.m.) VO(IV) binders of blood serum on the potentially insulin-enhancing compound VO(HPO)(2) (HPO, 2-hydroxypyridine-N-oxide): and VO(MPO)(2) (MPO, 2-mercaptopyridine-N-oxide), the speciation in the binary system VO(IV)-HPO and VO(IV)-MPO and in the ternary systems VO(IV)-HPO(MPO)-ligand B (B=oxalate, lactate, citrate or phosphate) was studied by pH-potentiometry. The stability constants of the complexes formed were determined in aqueous solution at I=0.2 M (KCl) and T=25 degrees C. The most probable binding modes of the complexes were determined by EPR method. The pyridine-N-oxides were found to form very stable bis complexes, which are predominant in the pH range 2-7. The results in the ternary systems demonstrate that only the citrate is a strong enough VO(IV) binder to compete with the carrier ligands. The binding ability of the high-molecular-mass (h.m.m.) serum proteins albumin and transferrin were also assessed and transferrin was found to be an efficient binder molecule. The actual solution state of these compounds in blood serum is compared with that of other insulin-mimic VO(IV) complexes.

Citric Acid↗
PubMed2003

Aluminum speciation studies in biological fluids. Part 9. A quantitative investigation of aluminum(III)-glutamate complex equilibria and their potential implications for aluminum metabolism and toxicity.

As a nonessential element, aluminum is likely to be toxic both at low usual dietary levels in the long run (chronic toxicity) and at high therapeutic levels in shorter periods of time (acute toxicity). In both situations, aluminum toxicity is a direct function of aluminum bioavailability, which is itself dependent on Al(3+) solubility and charge neutralization. Dietary acids, by their intrinsic acidity and coordinating capacity, can extend the pH range, thus the section of the gastrointestinal tract, within which the Al(3+) ion remains soluble, and also help Al(3+) diffusion across the intestinal epithelium through the formation of neutral complex species. The present work examines the impact of glutamic acid, an essential amino acid also widely used in industrial food and drinks, on aluminum speciation in the gastrointestinal tract and blood plasma. Complex formation between the Al(3+) ion and glutamate has first been investigated through potentiometric titrations, complex stoichiometries being then checked by ESI mass spectrometry and NMR measurements. A series of mono- and polynuclear species has been characterized, whose influence on aluminum distribution in vivo has been assessed by computer simulation. The capacity of glutamate to maintain Al(3+) ions in solution under normal dietary conditions is predicted to be intermediate between glycine-like amino acids and succinate on the one hand, and tartrate and malate on the other hand, its Al(3+) neutralization effect being similar to that of succinate, tartrate and malate. These results, which point to a potential aggravating role of glutamate on aluminum gastrointestinal absorption, substantiate recent observations made on rats. In spite of the moderate effect expected from glutamate on aluminum bioavailability under most aluminum-based therapies investigated, attention is therefore called to the risk of glutamic acid ingestion simultaneously to any aluminum therapeutic form. Incidentally, the former implication of 'the' aluminum glutamate complex in the transfer of aluminum through the blood-brain barrier of aluminum loaded rats may effectively be attributed to one of the species characterized here, but is of no significance at all to aluminum contamination in humans, even at most extreme levels.

Aluminum Compounds↗
PubMed2003

Study of aluminium concentration and speciation of surface water in four catchments in the Limousin region (France).

This study highlights the contamination of the upstream catchment of several rivers (Vienne, Gartempe, Vézère) in the Limousin (France) by aluminium in the absence of atmospheric pollution. The presence of acid soils on a granitic platform is a natural factor which contributes to the presence of protons and aluminium in water. In the Limousin, it seems that the presence of aluminium in surface water is due to a combination of natural factors: poor acid soils, numerous wet moors and peat bogs. It is currently difficult to evaluate the real impact of intensive cultivation of coniferous trees on the aluminium concentrations found in water in this area. In water, the concentration in total aluminium increases with a decrease in pH and an increase in organic matter. Despite, high concentrations of total aluminium at low pH (close to or lower than 6), the monomeric toxic forms of aluminium, computed with a speciation software, are always inferior to the toxic values for fish. Under such conditions, the concentration in aluminium recorded in some upstream catchments of the Limousin rivers may not cause damage to aquatic life.

Aluminum Compounds↗
PubMed1997

Complexation of copper(I) by thioamino acids. Implications for copper speciation in blood plasma.

There is mounting evidence that Cu(I) is the most important oxidation state of copper in many physiological systems. Research into Cu(I)-thioamino acid complex formation serves not only to improve the chelation therapy for treating copper intoxication but may also provide a better understanding of many facets of normal copper metabolism. Formation constants for the ternary mixed ligand complexes of Cu(I) with cysteine (Cys), glutathione (GSH) and penicillamine (Pen) are reported here for the first time. Potentiometric titrations, using techniques specially developed for the stabilization of aqueous Cu(I), were performed at 25 degrees C in 1.00 M (Na)Cl. It was found that precipitation severely limits the experimentally accessible pH range and, consequently, the computer analysis of the binary metal-ligand systems; however, it is also found that this is less of a problem when two different ligands are present. This latter fact permitted better models of the binary systems to be developed. The formation constants of Cu(I)-thioamino acids determined in this work were used in an improved computer simulation of copper speciation in blood plasma which, for the first time, incorporates redox equilibria.

Computer Simulation↗
PubMed1999

Aluminum speciation studies in biological fluids. Part 5. A quantitative investigation of A1(III) complex equilibria with desferrioxamine, 2,3-dihydroxybenzoic acid, Tiron, CP20 (L1), and CP94 under physiological conditions, and computer-aided assessment of the aluminum-mobilizing capacities of these ligands in vivo.

While the involvement of environmental aluminum toxicity in the advent of senile dementias is still debated, acute aluminum toxicity of iatrogenic origin is well documented. So far, the only treatment available against it has been desferrioxamine (DFO), which induces major side effects. New drugs are thus highly desirable, and possible DFO substitutes have already been considered through various techniques. An important test for such new drugs is to assess their A1-mobilizing capacity in vivo. This can be done by computer-aided speciation provided formation constants for the corresponding A1(III) complexes are known beforehand. The present work reports an investigation of A1(III) complex equilibria with five sequestering ligands including DFO, and predicts the respective capacities of these to mobilize aluminum in vivo under normal and inflammatory conditions.

1,2-Dihydroxybenzene-3,5-Disulfonic Acid Disodium ↗
PubMed2002

Modelling the physico-chemical speciation of plutonium in the eastern Irish Sea: a further development.

A numerical full three-dimensional model previously developed to simulate the physicochemical speciation of plutonium in the eastern Irish Sea has been improved. The model solves simultaneously the hydrodynamic equations, the suspended matter equation and the equations that give the time evolution of Pu concentrations in water, suspended matter and bottom sediments. It is considered that Pu may exist in each phase in two different oxidation states. Redox reactions are also considered. In the earlier version of the model, a one-step kinetic model was used to describe the transfers of radionuclides between the dissolved and solid phases. Although with this kind of model the contamination of the sediments can be properly simulated, it is clearly not able to describe the re-dissolution of radionuclides from a contaminated sediment once the external source to the sea is reduced. Thus, the model has been improved by substituting the one-step model with a two-step kinetic model consisting of two consecutive reversible reactions. Now it is possible to simulate both the sediment contamination and the re-dissolution processes.

Chemical Phenomena↗
PubMed2001

Speciation of rare earth elements in soil and accumulation by wheat with rare earth fertilizer application.

A greenhouse study was conducted to investigate the accumulation of rare earth elements (REEs), La, Ce, Pr and Nd, in winter wheat (Triticum aestivum L.), and the speciation of these elements in soil following the application of REE-based fertilizers. Improved crop yield was confirmed by the experiment. The accumulation behavior of La, Ce, Pr and Nd in wheat varied depending on the concentration of REE fertilizer application, i.e. increased with increasing REE concentration at low fertilization application, constant over the medium REE range, and decreased with increasing REE concentration at high fertilizer application. Significant negative correlation was obtained between REE contents in roots and soil pH (r = -0.5787 to -0.8442 for La). REEs in both the fertilized and unfertilized soils were fractionated by a three-stage sequential extraction procedure into three chemically distinct fractions: water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), and organic and sulfide bound (B3). REEs in fertilized soils were found mainly in the B2 and B3 fractions, with only a small amount in the B1 fraction. REEs in B1 and B2 fractions were negatively correlated with soil pH (r = -0.6892 to -0.8927 and -0.7462 to -0.9482). Significant correlation was obtained between REEs in B1 fraction and REE contents in root. The correlation coefficients ranged from 0.6159 to 0.7410 when fertilizer application was lower than 20.0 mg/kg soil. No acceptable relationship was observed between REE contents in shoot and any of the extractable fractions in soils.

China↗
PubMed2003

Changes of copper speciation in maize rhizosphere soil.

Chemical forms of copper in the rhizosphere and bulk soil of maize were investigated using rhizobox cultivation and sequential extraction techniques. The copper accumulations were also determined. The results demonstrated that there were continuous changes in copper fractionation within the maize rhizosphere. Initially, the amount of exchangeable copper increased before dropping below the initial level after 40 days or so. Carbonate associated copper followed a similar trend of change, but with a slower pace than the exchangeable copper. The increase in carbonate associated copper only become evident after 30 days, with the net loss occurring after 60 days. There were also initial increases in oxide bound copper as well as decreases in the organic matter associated copper, both followed by a turnover after 40-50 days. The accumulation of copper in the maize plant was found to be biomass dependent. The amount of accumulated copper absorbed in the plant material exceeded the initial quantity of the exchangeable copper in the soil, revealing a transformation from less bioavailable to more bioavailable fractions. During cultivation, decreases in redox potential and increases in pH, dissolved organic carbon (DOC), and microbial activity in the maize rhizosphere were observed. The change in copper speciation may result from root-induced changes in DOC, redox potential, and microbial activity in the rhizosphere.

Agriculture↗
PubMed1999

Effect of plant growth on copper solubility and speciation in soil solution samples.

The effect of plant growth on copper solubility and speciation was studied in a 10-week pot experiment. A copper-tolerant grass variety (Agrostis capillaris L. var. Parys Mountain) was grown in pots that contained either clean (copper-total approx. 30 mg kg(-1)) or copper contaminated soil (copper-total approx. 170 mg kg(-1)) at two pH levels (4.7 and 5.5). Also, similar pots without vegetation were included in the study. Due to the addition of NH(4)NO(3) fertilizer and subsequent nitrification of ammonia to nitrate, soil pH decreased from 4.7 to 3.5 and from 5.5 to 4, respectively. In the planted pots, soil pH recovered faster after depletion of NH(4)(+). This resulted in a decrease in the calcium solution concentrations and an increase in the dissolved organic carbon (DOC) concentrations in the planted pots. However, this was only observed in the clean soil; in the contaminated soil no difference in DOC levels between bare and planted pots was observed. Copper solubility in the contaminated soil was lower in the presence of plants; in the clean soil no differences were observed between the bare and planted pots. In the planted pots, copper activities in solution in both clean and contaminated soils were two orders of magnitude lower than in the bare pots. Copper activities in the non-planted contaminated soil reached potentially toxic levels ([Cu]+/-10(-5) to 10(-6) M) in contrast to the lower levels in the planted pots ([Cu]+/-10(-7) to 10(-10) M). Data and model results show that plant growth improves pH, DOC and calcium in solution to such an extent that both the total dissolved copper concentration and the free metal activity in soils can be reduced. This stresses the potential beneficial role of plants for the immobilization and detoxification of metals in contaminated soils.

Journal Article↗
PubMed2000

Assessment of the Pb and Cu in vitro availability in wines by means of speciation procedures.

The speciation of Pb and Cu in white and red table wines was investigated, in order to estimate their respective bioavailability to man. For this purpose, wines were subjected to in vitro gastrointestinal digestion, and the following properties were studied in the wines and in their gastric and intestinal digests: (1) the average conditional stability constant (Kav) of the strongest complexes (those inert to cathodic voltammetry) and of the respective ligand concentration (CCinert); (2) the distribution of the metal among the different bands of reverse phase high performance liquid chromatography (RP-HPLC) (groups of compounds of different molecular weight and/or polarity); (3) the total metal concentration and metal present in the soluble and in the dialyzable fractions of the digest. The CCinert of the red wines and the respective digests were much greater than those of the white wines and their digests. The conditional stability constants of the strongest soluble complexes after the digestion ranged between 5.9 and 6.1 for Pb. These parameters could not be determined for Cu. After the digestion the dialyzable metal fraction (a relative index of the metal potentially available for interaction with the inner biologic ligands) was only 16% of the total Pb in red wine, 62% in white Verde and 75% in white wine. For Cu the dialyzable metal fraction was 45% of the total metal in red wine, 64% in white Verde and 98% in white wine.

Calibration↗
PubMed2001

Heavy metal speciation and leaching behaviors in cement based solidified/stabilized waste materials.

A circuit board printing factory sludge containing high concentrations of copper, zinc and lead was stabilized and solidified (S/S) with different portions of ordinary Portland cement (OPC) and pulverized fly ash (PFA). The chemical speciation and leaching behavior of heavy metals in these cement-based waste materials were studied by different sequential extraction procedures, standard toxicity characteristic leaching procedure (TCLP) and progressive TCLP tests. The sequential extraction results showed that more than 80% of Cu, Pb and Zn were associated with Fraction 2 (weak acid soluble, extracted with 1M NaOAc at pH 5.0 with a solid to liquid ratio of 1:60). This indicated that the heavy metals could exist in the S/S matrix as metal hydrated phases or metal hydroxides precipitating on the surface of calcium silicate hydrates (C-S-H), PFA and sludge particles. The progressive TCLP test results and MINTEQA2 calculation also showed the importance of Cu and Zn oxides during the leaching process. The leaching behaviors of these metals in the S/S waste materials were mainly controlled by the alkaline nature and acid buffering capacity of the S/S matrix. During the progressive TCLP tests, the alkaline conditions and acid buffering capacity of the matrix decreased with the dissolution of calcium hydroxide and C-S-H, therefore, the leaching of heavy metals in the S/S waste materials increased. The leaching of heavy metals in the S/S materials can be considered as a pH dependent and corresponding metal hydroxide solubility controlled process.

Hydrogen-Ion Concentration↗
PubMed2000

Speciation of elements in NIST particulate matter SRMs 1648 and 1650

X-ray absorption fine structure (XAFS) spectra for S, Cl, V, Cr, Mn, Cu, Zn, As, Br, Cd and Pb and Mossbauer spectra for Fe have been obtained for two National Institute of Standards and Technology (NIST) particulate matter (PM) standard reference materials (SRMs): urban PM (SRM 1648) and diesel PM (SRM 1650). The spectral data, complemented by information on elemental concentrations from proton-induced X-ray-emission (PIXE) spectroscopy, were used to interpret the speciation of these elements in these complex materials. It appears that all the metallic elements investigated occur in oxidized forms, principally as sulfates in the diesel PM SRM and as sulfates, oxides, and possibly other forms (e.g. clays?) in the urban PM. A minor fraction of the sulfur and major fractions of the halogens, Cl and Br, occur as organosulfide (thiophene) and organohalide occurrences, respectively, that must be associated with the abundant carbonaceous matter that constitutes the major component of the two PM SRMs. Most of the sulfur, however, occurs as sulfate in the urban PM and as bisulfate in the diesel PM. In addition, elemental oxidation states have been determined directly by the spectroscopic techniques. Such information is often the key parameter in determining the toxicity and solubility of specific elements in PM, both of which are important in understanding the threat that such elements may pose to human health. For the two HAP elements, Cr and As, for which the toxicity depends greatly on oxidation state, the XAFS data showed that both elements are present in both SRMs predominantly in the less toxic oxidation states, Cr(III) and As(V). The potential of the XAFS spectra for use as source apportionment signatures is illustrated by reference to chromium, which exists in these two PM SRMs in very different forms.

Journal Article↗