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Environmental microbes can speciate and cycle arsenic.

Naturally occurring arsenic is found predominantly as arsenate [As(V)] or arsenite [As(III)], and can be readily oxidized or reduced by microorganisms. Given the health risks associated with arsenic in groundwater and the interest in arsenic-active microorganisms, we hypothesized that environmental microorganisms could mediate a redox cycling of arsenic that is linked to their metabolism. This hypothesis was tested using an As(V) respiring reducer (strain Y5) and an aerobic chemoautotrophic As(II) oxidizer (strain OL1 ) both isolated from a Superfund site, Onondaga Lake, in Syracuse, NY. Strains were grown separately and together in sealed serum bottles, and the oxic/anoxic condition was the only parameter changed. Initially, under anoxic conditions when both isolates were grown together, 2 mM As(V) was stoichiometrically reduced to As(III) within 14 days. Following complete reduction, sterile ambient air was added and within 24 h As(III) was completely oxidized to As(V). The anoxic-oxic cycle was repeated, and sterile controls showed no abiotic transformation within the 28-day incubation period. These results demonstrate that microorganisms can cycle arsenic in response to dynamic environmental conditions, thereby affecting the speciation, and hence mobility and toxicity of arsenic in the environment.

Anaerobiosis↗

Comparison of analytical techniques for dynamic trace metal speciation in natural freshwaters.

Several techniques for speciation analysis of Cu, Zn, Cd, Pb, and Ni are used in freshwater systems and compared with respect to their performance and to the metal species detected. The analytical techniques comprise the following: (i) diffusion gradients in thin-film gels (DGT); (ii) gel integrated microelectrodes combined to voltammetric in situ profiling system (GIME-VIP); (iii) stripping chronopotentiometry (SCP); (iv) flow-through and hollow fiber permeation liquid membranes (FTPLM and HFPLM); (v) Donnan membrane technique (DMT); (vi) competitive ligand-exchange/stripping voltammetry (CLE-SV). All methods could be used both under hardwater and under softwater conditions, although in some cases problems with detection limits were encountered at the low total concentrations. The detected Cu, Cd, and Pb concentrations decreased in the order DGT > or = GIME-VIP > or = FTPLM > or = HFPLM approximately = DMT (>CLE-SV for Cd), detected Zn decreased as DGT > or = GIME-VIP and Ni as DGT > DMT, in agreement with the known dynamic features of these techniques. Techniques involving in situ measurements (GIME-VIP) or in situ exposure (DGT, DMT, and HFPLM) appear to be appropriate in avoiding artifacts which may occur during sampling and sample handling.

Artifacts↗

Release of arsenic to the environment from CCA-treated wood. 1. Leaching and speciation during service.

Insufficient information exists about the speciation of arsenic leaching from in-service chromated copper arsenate (CCA)-treated products and the overall impact to soils and groundwater. To address this issue, two decks were constructed, one from CCA-treated wood and the other from untreated wood. Both decks were placed in the open environment where they were impacted by rainfall. Over a one-year period, rainwater runoff from the decks and rainwater infiltrating through 0.7 m of sand below the decks was collected and analyzed for arsenic species by HPLC-ICP-MS. The average arsenic concentration in the runoff of the untreated deck was 2-3 microg/L, whereas from the CCA-treated deck it was 600 microg/L. Both inorganic As(III) and As(V) were detected in the runoff from both decks, with inorganic As(V) predominating. No detectable levels of organoarsenic species were observed. The total arsenic concentration in the infiltrated water of the treated deck had risen from a background concentration of 3 microg/L to a concentration of 18 microg/L at the end of the study. Data from the deck study were combined with annual CCA-treated wood production statistics to develop a mass balance model to estimate the extent of arsenic leaching from in-service CCA-treated wood structures to Florida soils. Results showed that during the year 2000, of the 28 000 t of arsenic imported into the state and utilized for in-service CCA-treated wood products, approximately 4600 t had already leached. Future projections suggest that an additional 11,000 t of arsenic will leach during in-service use within the next 40 years.

Arsenates↗

Release of arsenic to the environment from CCA-treated wood. 2. Leaching and speciation during disposal.

Wood treated with chromated copper arsenate (CCA) is primarily disposed within construction and demolition (C&D) debris landfills, with wood monofills and municipal solid waste (MSW) landfills as alternative disposal options. This study evaluated the extent and speciation of arsenic leaching from landfills containing CCA-treated wood. In control lysimeters where untreated wood was used, dimethylarsinic acid (DMAA) represented the major arsenic species. The dominant arsenic species differed in the lysimeters containing CCA-treated wood, with As(V) greatest in the monofill and C&D lysimeters and As(III) greatest in the MSW lysimeters. In CCA-containing lysimeters, the organoarsenic species monomethylarsonic acid (MMAA) and DMAAwere virtually absent in the monofill lysimeter and observed in the C&D and MSW lysimeters. Overall arsenic leaching rate varied for the wood monofill (0.69% per meter of water added), C&D (0.36% per m), and MSW (0.84% per m) lysimeters. Utilizing these rates with annual disposal data, a mathematical model was developed to quantify arsenic leaching from CCA-treated wood disposed to Florida landfills. Model findings showed between 20 and 50 t of arsenic (depending on lysimeter type) had leached prior to 2000 with an expected increase between 350 and 830 t by 2040. Groundwater analysis from 21 Florida C&D landfills suspected of accepting CCA-treated wood showed that groundwater at 3 landfills was characterized by elevated arsenic concentrations with only 1 showing impacts from the C&D waste. The slow release of arsenic from disposed treated wood may account for the lack of significant impact to groundwater near most C&D facilities at this time. However, greater impacts are anticipated in the future given that the maximum releases of arsenic are expected by the year 2100.

Arsenates↗

Selenium speciation in kerogen from two Chinese selenium deposits: environmental implications.

Selenium is an essential trace element for humans, animals, and vegetation. Its occurrence in the environment is characterized by specific chemical and biochemical properties that control its elemental solubility, toxicity, and environmental behavior. The Laerma Se-Au deposit and Yutangba Se deposit are two important Se-bearing deposits found recently in China. In one of these areas (Yutangba), a serious environmental impact happened involving Se poisoning. Previous studies have shown that Se in both deposits is closely related to organic matter, especially kerogen fractions, but detailed relationships between Se and kerogen and Se chemical forms were not reported. In this study, the different speciation of Se is identified by transmission electron microscopy (TEM) and other geochemical techniques (infrared spectra (IS) and X-ray diffraction (XRD)) from kerogen samples extracted from ore rocks of both deposits. The occurrence of organically bound Se in the Laerma deposit and elemental Se nanograins in the Yutangba deposit is observed, indicating the diversity of formation mechanisms and possible chemical forms of Se in Se-rich rocks. The formation of elemental Se associated with organic matter is likely related to redox conditions, whereas organic species are related to the higher sulfur content of kerogen and possibly result from S-Se substitutions. This discovery provides new evidence with which to assess potential Se mobility during weathering of ore-bearing rocks. In an altered rock, the elemental Se in kerogen is more steadily mobilized and is potentially accumulated by vegetation, which may explain the sudden prevalence of Se poisoning in the Yutangba area. In contrast, organically bound Se seems more resistant to chemical alteration compared to other Se species so that its bioavailability may be very restricted.

Adsorption↗

Interactions between microbial iron reduction and metal geochemistry: effect of redox cycling on transition metal speciation in iron bearing sediments.

Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respectto Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HCl insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. In addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a -3x increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by approximately 12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These data suggest that in situ redox cycling may serve as an effective method for

Ferric Compounds↗

Strontium speciation during reaction of kaolinite with simulated tank-waste leachate: bulk and microfocused EXAFS analysis.

Radioactive strontium (90Sr) is an important constituent of the complex wastes from past nuclear weapons production and has been stored in underground tanks at U.S. DOE sites (e.g., Hanford, WA). Using bulk and microfocused EXAFS spectroscopy, we examined temporal changes in solid-phase Sr speciation in kaolinite samples reacted for 1-369 d with high-pH, high ionic strength synthetic tank-waste leachate containing Sr(2+) and Cs(+) at 10(-3) mol kg(-1). Analyses of bulk EXAFS spectra showed that Sr initially forms a precipitate by 7 d with a local structure similar to SrCO(3-) (s). At 33 d, microfocused EXAFS of individual particles in one sample revealed a mixture of hydrated and dehydrated Sr associated with neoformed sodalite-type phases. At aging times of 93 d and longer, bulk EXAFS spectra and supporting characterizations indicated nonexchangeable Sr with a local structure consistent with incorporation into increasingly crystalline aluminosilicate particles, particularly sodalite. These experimental studies suggest that irreversible trapping of radionuclides occurs if they are present during the formation and aging of feldspathoid alteration products of local Si-bearing sediment minerals. This may serve as an effective contaminant sequestration mechanism at sites such as Hanford.

Carbonates↗

Effect of bromide and iodide ions on the formation and speciation of disinfection byproducts during chlorination.

Two natural waters were fortified with various levels of bromide or iodide ions (0-30 microM) and chlorinated in the laboratory to study the impact of bromide and iodide ions on the formation and speciation of disinfection byproducts. Trihalomethanes (THMs), haloacetic acids (HAAs), total organic halogen (TOX), and its halogen-specific fractions total organic chlorine (TOCl), bromine (TOBr), and iodine (TOI), were measured in this work. The molar yields of THMs and HAAs increased as the initial bromide concentration increased. No significant change in TOX concentration was found for varying bromide concentrations. However, TOX concentrations decreased substantially with increasing initial iodide concentrations. At higher levels of bromide, there was a decreasing level of unknown TOX and unknown TOCl but an increasing level of unknown TOBr. The extent of iodine substitution was much lower than that of bromine substitution when comparing identical initial concentrations because a substantial amount of iodide was oxidized to iodate by chlorine. The tendency toward iodate formation resulted in the unusual situation where higher chlorine doses actually caused reduced levels of iodinated organic byproducts. Quantitative assessment of the results of this study showed a good agreement with kinetic data in the literature.

Acetic Acid↗

Development of a wet-chemical method for the speciation of iron in atmospheric aerosols.

The ability to quantify the chemical and physical forms of transition metals in atmospheric particulate matter (PM) is essential in determining potential human health and ecological effects. A method for the speciation of iron in atmospheric PM has been adapted which involves extraction in a well-defined solution followed by oxidation state specific detection. The method was applied to a suite of environmental aerosols. Ambient atmospheric aerosols in an urban area of St. Louis (the St. Louis-Midwest Supersite) were collected on Teflon substrates and were leached in one of four different solutions: (1) >18.0 Momega water; (2) 140 microM NaCl solution; (3) pH = 7.4 NaHCO3 solution; and (4) pH = 4.3 acetate buffering system. Fe(ll) was determined directly using the Ferrozine method as adapted to liquid waveguide spectrophotometry using a 1 m path-length cell. Fe(lll) was determined similarly after reduction to Fe(ll). It was found that, at low ionic strength, pH exerted a major influence on Fe(ll) solubility with the greatest Fe(ll) concentration consistently found in the pH = 4.3 acetate buffer. Soluble Fe(lll) (as defined by a 0.2 microm filter) varied little with extractant, which implies that most of the Fe(lll) detected was colloidal. To characterize well-defined materials for future reference, NIST standard reference materials were also analyzed for soluble Fe(ll) and Fe(lll). For all SRMs tested, a maximum of 2.4% of the total iron (Urban Dust 1649a) was soluble in pH = 4.3 acetate buffer. For calibration curves covering the ranges of 0.5-20 microg/L Fe(ll), excellent linearity was observed in all leaching solutions with R2 values of > 0.999. Co-located filters were used to test the effect of storage time on iron oxidation state in the ambient particles as a function of time. On two samples, an average Fe(ll) decay rate of 0.89 and 0.57 ng Fe(ll) g(-1) PM day(-1) was determined from the slope of the regression, however this decrease was determined not to be significant over 3 months (95% confidence). As an application of this method to mobile source emissions, size-resolved PM10 samples were collected at the inlet and outlet of the Caldecott Motor Vehicle Tunnel in northern California. These samples indicate that the coarse fraction (PM10-PM2.5) contains almost 50% of the total soluble Fe(ll) in the aerosol.

Aerosols↗

Changes in uranium speciation through a depth sequence of contaminated Hanford sediments.

The disposal of basic sodium aluminate and acidic U(VI)-Cu(ll) wastes in the now-dry North and South 300 A Process Ponds atthe Hanford site resulted in a groundwater plume of U(VI). To gain insight into the geochemical processes that occurred during waste disposal and those affecting the current and future fate and transport of this uranium plume, the solid-phase speciation of uranium in a depth sequence of sediments from the base of the North Process Pond through the vadose zone to groundwater was investigated using standard chemical and mineralogical analyses, electron and X-ray microprobe measurements, and X-ray absorption fine structure spectroscopy. Near-surface sediments contained uranium coprecipitated with calcite, which formed due to overneutralization of the waste ponds with base (NaOH). At intermediate depths in the vadose zone, metatorbernite [Cu(UO2PO4)2 x 8H2O] precipitated, likely during pond operations. Uranium occurred predominantly sorbed onto phyllosilicates in the deeper vadose zone and groundwater; sorbed uranium was also an important component at intermediate depths. Since the calcite-bearing pond sediments have been removed in remediation efforts, uranium fate and transport will be controlled primarily by desorption of the sorbed uranium and dissolution of metatorbernite.

Adsorption↗

Microprobe techniques for speciation analysis and geochemical characterization of mine environments: the mercury district of Almadén in Spain.

Metallurgic calcines with very high mercury and methylmercury content from the Almadén mining district were analyzed by synchrotron-based microprobe techniques. Information about mercury speciation was obtained by micro-EXAFS (microscopic extended X-ray absorption fine structure) spectroscopy, whereas elemental associations were evaluated by micro-XRF (microscopic X-ray fluorescence analysis) mapping. Complementary characterization methodologies, including X-ray diffraction (XRD), inductively coupled plasma-optical spectroscopy (ICP-OES), as well as a sequential extraction scheme (SES), were used to predict the potential availability of mercury. Analysis of total metal content revealed extremely high concentrations of mercury and iron (between 7 and 35 and 65-70 g kg(-1), respectively) and high zinc concentrations (2.2-2.5 g kg(-1)), whereas other metals such as copper, nickel, and lead were found at low concentration levels (30-300 mg kg(-1)). Micro-EXAFS results indicate that cinnabar (HgS(red)) is one of the main species within the studied mercury-rich particles (5-89% of total mercury content), together with more soluble mercury compounds such as Hg3(SO4)02 (schuetteite) and HgO (5-55% of total mercury content). Additionally, element-specific micro-XRF maps of selected mercury-rich particles in the studied samples revealed an evident correlation among Hg-Pb-Ni (and S), indicating a possible geochemical linkage of these elements. Correlations were also found among Fe-Mn and Hg, which have been attributed to sorption of mercury onto oxyhydroxides of Fe and Mn. This finding was supported by results from a sequential extraction scheme, where a significant

Environmental Monitoring↗

Trace metal speciation in brackish water using diffusive gradients in thin films and ultrafiltration: comparison of techniques.

Diffusive gradients in thin films (DGT) and ultrafiltration were used to measure trace metal concentrations in the Baltic Sea. The results provide the first comparison of these two fundamentally different speciation methods for trace metals. Cd, Cu, Mn, Ni, and Zn were measured at two sites with different total trace metal concentrations. DGT units prepared with APA-gel as diffusive layer and Chelex 100 resin as binding agent were used throughout the study. The ultrafiltration was performed with Millipore Prep/Scale modules with cutoffs of 1 and 10 kDa. Concentration levels of Mn, Zn, and Cd measured by DGT agreed with the concentrations measured in 1 kDa ultrafiltered samples. For Cu and Ni the ultrafiltered concentrations exceeded the DGT-labile concentrations. The ability of DGT to preconcentrate metals was found to be an analytical advantage compared with ultrafiltration. DGT appears to be a good alternative to 1 kDa ultrafiltration for measurement of truly dissolved Mn, Cd, and Zn in the Baltic Sea.

Diffusion↗

Arsenic sequestration in iron plaque, its accumulation and speciation in mature rice plants (Oryza sativa L.).

A compartmented soil-glass bead culture system was used to investigate characteristics of iron plaque and arsenic accumulation and speciation in mature rice plants with different capacities of forming iron plaque on their roots. X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure were utilized to identify the mineralogical characteristics of iron plaque and arsenic sequestration in plaque on the rice roots. Iron plaque was dominated by (oxyhydr)oxides, which were composed of ferrihydrite (81-100%), with a minor amount of goethite (19%) fitted in one of the samples. Sequential extraction and XANES data showed that arsenic in iron plaque was sequestered mainly with amorphous and crystalline iron (oxyhydr)oxides, and that arsenate was the predominant species. There was significant variation in iron plaque formation between genotypes, and the distribution of arsenic in different components of mature rice plants followed the following order: iron plaque > root > straw > husk > grain for all genotypes. Arsenic accumulation in grain differed significantly among genotypes. Inorganic arsenic and dimethylarsinic acid (DMA) were the main arsenic species in rice grain for six genotypes, and there were large genotypic differences in levels of DMA and inorganic arsenic in grain.

Absorptiometry, Photon↗

A new dinuclear vanadium(V)-citrate complex from aqueous solutions. Synthetic, structural, spectroscopic, and pH-dependent studies in relevance to aqueous vanadium(V)-citrate speciation.

Vanadium interactions with low molecular mass binders in biological fluids entail the existence of vanadium species with variable chemical and biological properties. In the course of efforts to elucidate the chemistry related to such interactions, we have explored the oxidative chemistry of vanadium(III) with the physiologically relevant tricarboxylic citric acid. Aqueous reactions involving VCl(3) and anhydrous citric acid, at pH approximately 7, resulted in blue solutions. Investigation into the nature of the species arising in those solutions revealed, through UV/visible and EPR spectroscopies, oxidation of vanadium(III) to vanadium(IV). Further addition of H(2)O(2) resulted in the oxidation of vanadium(IV) to vanadium(V), and the isolation of a new vanadium(V)-citrate complex in the form of its potassium salt. Analogous reactions with K(4)[V(2)O(2)(C(6)H(4)O(7))(2)].6H(2)O and H(2)O(2) or V(2)O(5) and citrate at pH approximately 5.5 afforded the same material. Elemental analysis pointed to the molecular formulation K(4)[V(2)O(4)(C(6)H(5)O(7))(2)].5.6H(2)O (1). Complex 1 was further characterized by FT-IR and X-ray crystallography. 1 crystallizes in the triclinic space group P(-)1, with a = 11.093(4) A, b = 9.186(3) A, c = 15.503(5) A, alpha = 78.60(1) degrees, beta = 86.16(1) degrees, gamma = 69.87(1) degrees, V = 1454.0(8) A(3), and Z = 2. The X-ray structure of 1 reveals the presence of a dinuclear vanadium(V)-citrate complex containing a V(V)(2)O(2) core. The citrate ligands are triply deprotonated, and as such they bind to vanadium(V) ions, thus generating a distorted trigonal bipyramidal geometry. Binding occurs through the central alkoxide and carboxylate groups, with the remaining two terminal carboxylates being uncoordinated. One of those carboxylates is protonated and contributes to hydrogen bond formation with the deprotonated terminal carboxylate of an adjacent molecule. Therefore, an extended network of hydrogen-bonded V(V)(2)O(2)-core-containing dimers is created in the lattice of 1. pH-dependent transformations of 1 in aqueous media suggest its involvement in a web of vanadium(V)-citrate dinuclear species, consistent with past solution speciation studies investigating biologically relevant forms of vanadium.

Journal Article↗

Speciation of ternary cobalt(II) phenanthroline-silica surface complexes as a function of pH and ligand steric bulk.

Co(II) solution species containing 1 equiv of phenanthroline (phen), 2-methyl-1,10-phenanthroline (MMP), or 2,9-dimethyl-1,10-phenanthroline (DMP) ligand formed inner-sphere surface complexes when grafted on silica. The speciation on the silica surface depended on both the pH of the grafting solution and the steric bulk of the ligand. [Co(DMP)](2+) formed tetrahedral surface adducts exclusively, with a 1:1 ligand-Co ratio. These surface adducts were first detectable at pH values above 5.1. [Co(MMP)](2+) and [Co(phen)](2+) formed exclusively octahedral adducts on the surface with a 1:1 ligand-Co ratio at pH values below 5. The [Co(MMP)](2+) complex formed a tetrahedral adduct initially at pH 6 and increasingly as the pH was raised. The [Co(phen)](2+) complex did not produce a comparable tetrahedral surface species under any conditions. Instead, mixtures of octahedral surface species with both 1:1 and 2:1 ligand-Co ratios began to form at pH values above 6. Taken together, the results indicated that the development of tetrahedral stereochemistry was strongly influenced by steric factors in the presence of a nitrogen-donating ligand. All three phenanthroline derivatives promoted surface binding of the Co(II) ion adducts, so that maximal binding occurred at lower pH values than for binding of [Co(H(2)O)(6)](2+), which formed exclusively tetrahedral adducts.

Journal Article↗

A new dinuclear Ti(IV)-peroxo-citrate complex from aqueous solutions. Synthetic, structural, and spectroscopic studies in relevance to aqueous titanium(IV)-peroxo-citrate speciation.

The wide use of titanium in applied materials has prompted pertinent studies targeting the requisite chemistry of that metal's biological interactions. In order to understand such interactions as well as the requisite titanium aqueous speciation, we launched investigations on the synthesis and spectroscopic and structural characterization of Ti(IV) species with the physiological citric acid. Aqueous reactions of TiCl(4) with citric acid in the presence of H(2)O(2) and neutralizing ammonia afforded expediently the red crystalline material (NH(4))(4)[Ti(2)(O(2))(2)(C(6)H(4)O(7))(2)].2H(2)O (1). Complex 1 was further characterized by UV-vis, FT-IR, FT- and laser-Raman, NMR, and finally by X-ray crystallography. Compound 1 crystallizes in the monoclinic space group P2(1)/n, with a = 10.360(4) A, b = 10.226(4) A, c = 11.478(6) A, beta = 107.99(2) degrees, V = 1156.6(9) A(3), and Z = 2. The X-ray structure of 1 reveals a dinuclear anionic complex containing a Ti(IV)(2)O(2) core. In that central unit, two fully deprotonated citrate ligands are coordinated to the metal ions through their carboxylate moieties in a monodentate fashion. The central alkoxides serve as bridges to the two titanium ions. Also attached to the Ti(IV)(2)O(2) core are two peroxo ligands each bound in a side-on fashion to the respective metal ions. NH(4)(+) ions neutralize the 4- charge of the anion in 1, further contributing to the stability of the derived lattice through H-bond formation. The structural similarities and differences with congener vanadium(V)-peroxo-citrate complexes may point out potential implications in the chemistry of titanium with physiological ligands, when the former is present in a biologically relevant medium.

Citrates↗

Titanium(IV) citrate speciation and structure under environmentally and biologically relevant conditions.

The water-soluble complexes of Ti(IV) with citrate are of interest in environmental, biological, and materials chemistry. The aqueous solution speciation is revealed by spectropotentiometric titration. From pH 3-8, given at least three equivalents of ligand, 3:1 citrate/titanium complexes predominate in solution with successive deprotonation of dangling carboxylates as the pH increases. In this range and under these conditions, hydroxo- or oxo-metal species are not supported by the data. At ligand/metal ratios between 1:1 and 3:1, the data are difficult to fit, and are consistent with the formation of such hydroxo- or oxo- species. Stability constants for observed species are tabulated, featuring log beta-values of 9.18 for the 1:1 complex [Ti(Hcit)](+), and 16.99, 20.41, 16.11, and 4.07 for the 3:1 complexes [Ti(H(2)cit)(3)](2-), [Ti(H(2)cit)(Hcit)(2)](4-), [Ti(Hcit)(2)(cit)](6-), and [Ti(cit)(3)](8-), respectively (citric acid = H(4)cit). Optical spectra for the species are reported. The complexes exhibit similar yet distinct spectra, featuring putative citrate-to-Ti(IV) charge-transfer absorptions (lambda(max) approximately 250-310 nm with epsilon approximately 5000-7000 M(-)(1) cm(-1)). The prevailing 3:1 citrate/titanium ratio in solution is supported by electrospray mass spectrometry data. The X-ray crystal structure of a fully deprotonated tris-citrate complex Na(8)[Ti(C(6)H(4)O(7))(3)].17H(2)O (1) (or Na(8)[Ti(cit)(3)].17H(2)O) that crystallizes from aqueous solution at pH 7-8 is reported. Compound 1 crystallizes in the triclinic space group P, with a = 11.634(2) Angstroms, b = 13.223(3) Angstroms, c = 13.291(3) Angstroms, V = 1982.9(7) Angstroms(3), and Z = 2.

Citrates↗

pH-specific aqueous synthetic chemistry in the binary cadmium(II)-citrate system. Gaining insight into cadmium(II)-citrate speciation with relevance to cadmium toxicity.

The involvement of Cd(II) in toxic manifestations and pathological aberrations in lower and higher organisms entails interactions with low and high molecular mass biological targets. To understand the relevant chemistry in aqueous media, we have launched pH-dependent synthetic efforts targeting Cd(II) with the physiological ligand citric acid. Reactions of Cd(II) with citric acid upon the addition of NaOH at pH 2.5 and pyridine at pH 3 and the addition of ammonia at pH approximately 7 led to the new complexes [Cd3(C6H5O7)2(H2O)5] x H2O (1) and (NH4)[Cd(C6H5O7)(H2O)] x H2O (2), respectively. Complexes 1 and 2 were characterized by elemental analysis, spectroscopy (FT-IR and NMR), and X-ray crystallography. Complex 1 crystallizes in the monoclinic space group P2(1)/n, with a = 18.035(6) A, b = 10.279(4) A, c = 12.565(4) A, beta = 109.02(1) degrees, V = 2202(2) A3, and Z = 4. Complex 2 crystallizes in the monoclinic space group P2(1), with a = 9.686(4) A, b = 8.484(4) A, c = 7.035(3) A, beta = 110.28(1) degrees, V = 542.3(4) A3, and Z = 2. Complex 1 is a trinuclear assembly with the citrate ligand securing a stable metallacyclic ring around one Cd(II), with the terminal carboxylates spanning into the coordination sphere of two nearby Cd(II) ions. Complex 2 contains mononuclear units of Cd(II) bound by citrate in an overall coordination number of 8. In both 1 and 2, the participating citrates exhibit three different modes of coordination, thus projecting a distinct yet variable aqueous structural chemistry of Cd(II) with physiological substrates. The pH-dependent chemistry and its apparent structural diversity validate past solution speciation studies, projecting the existence of mononuclear species such as the one in the anion of 2. The spectroscopic and structural properties of 2 emphasize the significance of the information emerging from synthetic studies that otherwise would not have been revealed through conventional solution studies, while concurrently shedding light onto the linkage of the requisite chemistry with the potential biological toxicity of Cd(II).

Cadmium↗