Lead Solubility and Mineral Structures of Coprecipitated Lead/Calcium Oxalates.

Low-molecular-weight organic acids such as oxalate, which are ubiquitous in the environment, can control the solubility and bioavailability of toxic metals such as Pb in soils and water by influencing complexation and precipitation reactions. Here, we investigated Pb solubility in relation to Pb-oxalate precipitation at pH 5.0 in the absence and presence of calcium (Ca), a common cation in environmental matrices. At Pb mole fractions less than 0.10, sequestration of Pb into Ca oxalate to form a solid solution substantially lowered Pb solubility relative to that of pure Pb oxalate to an extent inversely proportional to the Pb mole fraction. Small Pb/Ca solid-solution distribution coefficients at these low mole ratios was largely attributed to the stronger complexation of Pb compared to Ca with oxalate to form soluble metal-oxalate complexes, which in turn limited Pb incorporation into the Ca-oxalate crystal lattice. Characterization of the Pb/Ca-oxalate coprecipitates by X-ray diffraction, optical microscopy, and Fourier transform infrared spectroscopy revealed that the whewellite (Ca-oxalate monohydrate) structure was destabilized by substitution of small amounts of Pb into the lattice, and thus, the formation of the Ca-oxalate dihydrate (weddellite) was favored over the monohydrate. At Pb mole fractions above 0.20, discrete crystallites of Pb oxalate were identified. These new findings imply that Pb/Ca-oxalate coprecipitates in the presence of Ca could reduce the solubility of Pb in Pb-contaminated acid soils.

Oxalate-enhanced solubility of lead (Pb) in the presence of phosphate: pH control on mineral precipitation.

Here we study the precipitation of lead (Pb)-phosphate minerals over the pH range of 4.0 to 8.0 with and without oxalate, a ubiquitous and abundant low-molecular-weight organic acid derived from plants and microorganisms in environmental matrices. In the aqueous Pb-phosphate systems, phosphate precipitated Pb efficiently, reducing the dissolved Pb concentration below 1 µM at all the tested pH values, with the minimum solubility of about 0.1 µM measured at the intermediate pH of 6.0. The measured dissolved Pb and free Pb2+ ion activity were not in agreement with predictions from generally-accepted solubility products of the Pb phosphate minerals, particularly hydroxypyromorphite [Pb5(PO4)3OH]. Discrepancies between our measured Pb phosphate solubility products and older reported values are attributed to non-ideal behavior of these minerals (incongruent dissolution) as well as uncertainties in stability constants for soluble Pb-phosphate ion pairs. The presence of equimolar levels of oxalate and phosphate resulted in up to 250-fold increase in Pb solubility at acidic pH and about a 4-fold increase at pH 7.0, due to the strong suppression of Pb phosphate precipitation by oxalate and formation of soluble Pb-oxalate complexes. At pH 4.0 and 5.0, Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) identified a Pb-oxalate mineral phase as the only precipitate despite the presence of phosphate; in the absence of oxalate, Pb hydrogen phosphate, PbHPO4, stably formed under these acidic conditions. At pH 6.0 and greater, FTIR and XRD data revealed that Pb-phosphate [Pb3(PO4)2], and hydroxypyromorphite [Pb5(PO4)3OH] to a lesser extent, were the predominant precipitates both in the absence and presence of oxalate. Therefore, oxalate did not strongly interfere with Pb-phosphate mineral formation at aqueous pH greater than 6.0 but oxalate controlled Pb solubility at acidic pH values.

Structures and mechanisms in clay nanopore trapping of structurally-different fluoroquinolone antimicrobials.

Smectite clay nanoparticles are implicated in the retention of antimicrobials within soils and sediments; these clays are also inspected as drug carriers in physiological systems. Cation exchange is considered the primary adsorption mechanism of antimicrobials within smectite nanopores. However, a dual role of acid-base chemistry and adsorptive structures is speculated by recent studies. Using the prototypical smectite clay montmorillonite, we employed a combination of X-ray diffraction (XRD), nuclear magnetic resonance, attenuated total reflectance-Fourier transform infrared spectroscopy, and molecular dynamics simulations to investigate the interlayer nanopore trapping of two structurally-different fluoroquinolone (FQ) antimicrobials with similar acid-base chemistry: ciprofloxacin (a first-generation FQ) and moxifloxacin (a third-generation FQ). Greater sorption at pH 5.0 than at pH 7.0 for both FQs was consistent with cation-exchange of positively-charged species. However, the clay exhibited a near twofold higher sorption capacity for moxifloxacin than for ciprofloxacin. This difference was shown by the XRD data to be accompanied by enhanced trapping of moxifloxacin within the clay interlayers. Using the XRD-determined nanopore sizes, we performed molecular dynamics simulations of thermodynamically-favorable model adsorbates, which revealed that ciprofloxacin was adsorbed parallel to the clay surface but moxifloxacin adopted a tilted conformation across the nanopore. These conformations resulted in more slowly-exchanged than quickly-exchanged Na complexes with ciprofloxacin compared with moxifloxacin. These different Na populations were also captured by 23Na nuclear magnetic resonance. Furthermore, the simulated adsorbates uncovered different complexation interactions that were corroborated by infrared spectroscopy. Therefore, beyond acid-base chemistry, our findings imply that distinct adsorbate structures control antimicrobial trapping within clay nanopores, which can promote persistence in environmental matrices and stable delivery in biological systems.

Solubility, structure, and morphology in the co-precipitation of cadmium and zinc with calcium-oxalate.

Calcium-oxalates (Ca-Ox), which are widely produced by microorganisms and plants, are ubiquitous and persistent biominerals in the biosphere. We investigated the potential trapping of two phytotoxic metals, cadmium (Cd) and zinc (Zn) by isomorphous substitution into the crystalline structure of Ca-Ox precipitated over a wide range of Cd2+/Ca2+ or Zn2+/Ca2+ ratio in solution. We employed atomic absorption spectroscopy, X-ray diffraction (XRD), and optical microscopy to evaluate our hypotheses that favorable solid-solution conditions and structural framework of crystal habits promote selective metal trapping within Ca-Ox precipitates. Chemical analysis demonstrated more effective Cd-Ox/Ca-Ox than Zn-Ox/Ca-Ox co-precipitate formation at the same trace metal mole fraction in solution. The XRD results revealed sequestration of Cd, but not Zn, within Ca-Ox monohydrate (whewellite). Comparative chemical analysis with Cd-Ox formation in the absence of Ca-Ox showed that the whewellite solid-solution formation lowered the solubility of Cd2+ below that of pure Cd-Ox. The XRD patterns indicated that Zn2+ precipitated as a separate pure Zn-Ox crystal that is largely excluded from the Ca-Ox structure. Furthermore, the presence of Zn2+ in solution favored the formation of the less stable Ca-Ox dihydrate (weddellite) over whewellite. In agreement with the XRD data, visualization of the co-precipitates by optical microscopy illustrated combined mineral phases of Cd-Ox with Ca-Ox whereas Zn-Ox and Ca-Ox exhibited two distinct mineral morphologies. Our findings shed light into the structural factors that are most critical in facilitating the trapping of toxic trace metals within Ca-Ox crystals.