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Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater.

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium [Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.

Cations, Divalent↗

Growth stimulatory precipitates of Ca2+ and pyrophosphate.

Inorganic pyrophosphate (PPi) forms an insoluble precipitate with calcium in growth medium when its concentration exceeds about 0.1 mM. This PPi precipitate can reproduce the effects of 10% calf serum on all cell processes examined in Balb/c 3T3 cells, including hexose uptake and metabolism to lactate, 3H-uridine, and 3H-choline uptake, and the incorporation of 3H-leucine and 3H-thymidine into trichloroacetic acid (TCA)-insoluble material. Concentrations of PPi insufficient to form a precipitate are without effect on cell metabolism. The precipitates are most effective when prepared with concentrations of PPi just sufficient to result in precipitate formation and become considerably less effective as the PPi concentration increases, even though the quantity of precipitate formed continues to increase with PPi concentration up to 1 mM PPi. Precipitates formed at low PPi concentrations consist largely of Ca2+ (81% of cations), PPi (77% of anions), and Pi (23% of anions). Precipitates formed with higher concentrations of PPi contain proportionately less Ca2+ and Pi and more monovalent cations and PPi. We have distinguished cell surface-bound PPi from intracellular PPi by differential extraction. The quantity of surface-bound PPi increases sharply when the PPi concentration reaches the point of precipitate formation. If the precipitate is prevented from binding to the cell surface by inverting monolayer cultures in precipitate-containing medium, the cells are not stimulated. These findings suggest that the binding of PPi precipitate to the cell surface is involved in the stimulation of cell metabolism by PPi. PPi precipitates do not absorb serum mitogens or inhibitors from the culture medium, nor do they affect the binding of 125I-platelet-derived growth factor to its specific cell-surface receptor, suggesting that PPi precipitates do not act directly through either of these mitogen-receptor systems. In analogy to cell stimulation by epidermal growth factor and by antigens, we suggest that PPi may be active only in the form of a precipitate because multivalent binding of receptors with formation of clusters is required for stimulation. The inhibitory effects of high concentrations of PPi may be due to interference by free PPi with formation of active receptor clusters.

Animals↗

Magnetite seeded precipitation of phosphate.

Seeded precipitation of Ca phosphate on magnetite mineral (Fe3O4) surfaces was investigated using a Jar Test system in supersaturated solutions at 20 degrees C and ionic strength 0.01 mol l(-1) with relative super saturation, 12.0-20.0 for HAP. pH of the solution, initial phosphorus concentration and molar Ca/P ratio were investigated as the main parameters, which effect the seeded precipitation of Ca phosphate. Results showed that there is no pronounced effect of magnetite seed, neither positive nor negative on the amount of calcium phosphate precipitation. pH was found to be the main parameter that determines the phosphate precipitated onto the seed surface. Increasing of the pH of precipitation reaction was resulted in the decrease in percentage amount of phosphate precipitated onto seed surfaces to total precipitation (magnetite seeded precipitation efficiency). It was concluded that the pH dependence of magnetite-seeded precipitation should be considered in the light of its effect on the supersaturated conditions of solution. Saturation index (SI) of solution with respect to the precipitate phase was considered the driving force for the precipitation. A simulation programme PHREEQC (Version 2) was employed to calculate the Saturation-index with respect to hydroxyapatite (HAP) of the chemically defined precipitation system. It was found a good relationship between SI of solution with respect to HAP and the magnetite seeded precipitation efficiency, a second order polynomial function. Results showed that more favorable solution conditions for precipitation (higher SI values of solution) causes homogenous nucleation whereas heterogeneous nucleation led to a higher magnetite seeded precipitation efficiency.

Chemical Precipitation↗

Interactions between precipitating and nonprecipitating antibodies in the formation of immune complexes.

In the present study, we used monoclonal antidinitrophenol (DNP) antibodies to determine certain of the biophysical characteristics of precipitating and nonprecipitating antibodies. In addition, we studied the dynamics of immune complex (IC) formation when precipitating antibodies react with antigen in the presence of nonprecipitating antibodies. The antigen utilized in these studies was DNP-bovine serum albumin. All isolated nonprecipitating anti-DNP antibodies were of the IgG2b isotype, whereas all antibodies with other isotypes (IgG1, IgG3, IgM, IgA and IgE) were precipitating. Nonprecipitating antibodies did not differ significantly from precipitating antibodies in affinity, valence, or isoelectric point. Nonprecipitating antibodies inhibited the formation of precipitable IC between antigen and precipitating antibodies. In addition, preformed IC precipitates were solubilized by nonprecipitating antibodies. The solubilization of IC precipitates was influenced by the isotype of the precipitating antibody and by the antibody:antigen ratio in the IC precipitate. By isokinetic sucrose density centrifugation, we determined that solubilization of IC precipitates by nonprecipitating antibodies was associated with release of free precipitating antibody and formation of soluble IC between the antigen and the nonprecipitating antibody. In conclusion, in this study the nonprecipitating property of mouse anti-DNP antibodies is isotype-specific. Nonprecipitating antibodies compete and displace precipitating antibodies from the antigen, resulting in inhibition of IC precipitation and in IC solubilization. On the basis of the present results, we postulate that antibody-antibody interactions are important determinants of precipitating ability, and that these interactions are a characteristic of antibody isotype.

Animals↗

Precipitable immune complexes in Hodgkin's disease.

Sera from 28 untreated patients with Hodgkin's disease and from 120 healthy controls were investigated for the presence of circulating immune complexes using a modified 3% polyethylene glycol precipitation method with subsequent quantification of the precipitated protein. Elevated levels of precipitable protein were found in 79% (p less than 0.005) of Hodgkin's disease sera. The degree of elevation was associated with disease activity including the presence of B-symptoms. Constant and pronounced increase of precipitable protein was found in six patients with stage-III B nodular sclerosis subtype, thus exceeding the average amount of precipitable protein in healthy controls by a factor of 3-4. The erythrocyte sedimentation rate in 20 patients correlated with the amount of precipitable protein (r = 0.79). Additionally, partial component analysis of the precipitates was carried out by laser nephelometry. Immunoglobulins and complement components were identified as being major components of the precipitated material in sera both from patients and healthy controls, thus confirming the probability of the immune complex nature of the precipitates. Significant differences between patients and healthy controls concerned the amount of precipitable components. Elevation of precipitable IgM was found to be the most sensitive parameter (86% above means + 2 SD of normal controls, p less than 0.005). Increased amounts of precipitable IgG, C4, and Clq were found in 57-46% of patients' sera. Elevation of precipitable IgA and C3c were identified less often. The results suggest the quantification of precipitable immune complexes and their components to be of value as adjuncts in determining disease activity in Hodgkin's disease.

Adolescent↗