Role of assisted natural remediation in environmental cleanup

The apatite-group minerals of the general formula, M10(ZO4)6X2 (M = Ca, Sr, Pb, Na…, Z = P, As, Si, V…, and X = F, OH, Cl…), are remarkably tolerant to structural distortion and chemical substitution, and consequently are extremely diverse in composition (e.g., Kreidler and Hummel 1970; McConnell 1973; Roy et al. 1978; Elliott 1994). Of particular interest is that a number of important geological, environmental/paleoenvironmental, and technological applications of the apatite-group minerals are directly linked to their chemical compositions. It is therefore fundamentally important to understand the substitution mechanisms and other intrinsic and external factors that control the compositional variation in apatites.

The minerals of the apatite group are listed in Table 1⇓, and representative compositions of selected apatite-group minerals are given in Table 2⇓. Also, more than 100 compounds with the apatite structure have been synthesized (Table 3⇓). Phosphate apatites, particularly fluorapatite and hydroxylapatite, are by far the most common in nature and are often synonymous with “apatite(s)”. For example, fluorapatite is a ubiquitous accessory phase in igneous, metamorphic, and sedimentary rocks and a major constituent in phosphorites and certain carbonatites and anorthosites (McConnell 1973; Dymek and Owens 2001). Of particular importance in biological systems, hydroxylapatite and fluorapatite (and their carbonate-bearing varieties) are important mineral components of bones, teeth and fossils (McConnell 1973; Wright et al. 1984; Grandjean-Lecuyer et al. 1993; Elliott 1994; Wilson et al. 1999; Suetsugu et al. 2000; Ivanova et al. 2001).

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 Table 1. 
Summary of the apatite-group minerals



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 Table 2. 
Representative compositions and unit-cell parameters of selected apatite-group minerals.



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 Table 3. 
Formulas of selected synthetic compounds with the apatite structure.



Following Fleischer and Mandarino (1995), Table 1⇑ also includes melanocerite-(Ce), tritomite-(Ce), and tritomite-(Y), the compositions …

Compositions of the Apatite-Group Minerals: Substitution Mechanisms and Controlling Factors

Field evaluation of in situ remediation of a heavy metal contaminated soil using lime and red-mud.

https://naldc.nal.usda.gov/download/47864/PDF

Evaluation of chemical immobilization treatments for reducing heavy metal transport in a smelter-contaminated soil.

The effect of pH-increases due to Ca(OH)2 and KOH addition on the adsorption of cadmium (Cd) was examined in two soils which varied in their variable-charge components. The effect of Ca(OH)2 on immobilization and phytoavailability of Cd from one of the soils, treated with various levels of Cd (0–10 mg Cd kg−1 soil), was further evaluated using mustard (Brassica juncea L.) plants. Cadmium immobilization in soil was evaluated by a chemical fractionation scheme. The addition of Ca(OH)2 and KOH increased the soil pH, thereby increasing the adsorption of Cd, the effect being more pronounced in the soil dominated by variable charge components. There was a greater increase in Cd2+ adsorption in the KOH-treated than the Ca(OH)2-treated soil, which is attributed to the greater competition of Ca2+ for adsorption. Increasing addition of Cd enhanced Cd concentration in plants, resulting in decreased plant growth (i.e., phytotoxicity). Although addition of Ca(OH)2 effectively reduced Cd phytotoxicity, Cd uptake increased at the highest level, probably due to decreased Cd2+ adsorption resulting from increased Ca2+ competition. There was a significant inverse relationship between dry matter yield and Cd concentration in soil solution. Addition of Ca(OH)2 decreased the concentration of the soluble + exchangeable Cd fraction but increased the concentration of inorganic-bound Cd fractions in soil. Since there was no direct evidence for CdCO3 or Cd(OH)2 precipitation in the variable charge soil used for the plant growth experiment, alleviation of phytotoxicity can be attributed primarily to immobilization of Cd by enhanced pH-induced increases in negative charge.

Immobilization and phytoavailability of cadmium in variable charge soils. II. Effect of lime addition

The current study investigated the sorption and desorption of dissolved lead (Pb), cadmium (Cd) and zinc (Zn) from aqueous solutions and a contaminated soil by North Carolina mineral apatite. Aqueous solutions of Pb, Cd, and Zn were reacted with the apatite, followed by desorption experiments under a wide variety of pH conditions ranging from 3 to 12, including the extraction fluids used in the Toxicity Characteristic Leaching Procedure (TCLP) of the United States Environmental Protection Agency (US EPA). The sorption results showed that the apatite was very effective in retaining Pb and was moderately effective in attenuating Cd and Zn at pH 4–5. Approximately 100% of the Pb applied was removed from solutions, representing a capacity of 151 mg of Pb/g of apatite, while 49% of Cd and 29% of Zn added were attenuated, with removal capacities of 73 and 41 mg g-1, respectively. The desorption experiments showed that the sorbed Pb stayed intact where only 14–23% and 7–14% of the sorbed Cd and Zn, respectively, were mobilized by the TCLP solutions. The apatite was also effective in removing dissolved Pb, Cd, and Zn leached from the contaminated soil using pH 3–12 solutions by 62.3–99.9, 20–97.9, and 28.6–98.7%, respectively. In particular, the apatite was able to reduce the metal concentrations in the TCLP-extracted soil leachates to below US EPA maximum allowable levels, suggesting that apatite could be used as a cost-effective option to remediating metal-contaminated soils, wastes, and/or water. The sorption mechanisms are variable in the reactions between the apatite and dissolved Pb, Cd, and Zn. The Pb removals primarily resulted from the dissolution of the apatite followed by the precipitation of hydroxyl fluoropyromorphite. Minor otavite precipitation was observed in the interaction of the apatite with aqueous Cd, but other sorption mechanisms, such as surface complexation, ion exchange, and the formation of amorphous solids, are primarily responsible for the removal of Zn and Cd.

Evaluation of heavy metal remediation using mineral apatite

: Adsorption isotherm experiments using varying amounts of different apatites and a 10:1 water to soil ratio were used in combination with a thermodynamic model to determine the amount of apatite necessary to treat a given soil. These experiments suggested that soils may be remediated by extrapolating from the isotherm experiments, which equates to 10-50 kg of apatite per treated ton of soil, or less than 1% by weight. By comparison, grouting techniques can require as much as 30% to 50% by weight, depending upon the porosity of the soil.

/pdf/in-situ-immobilization-of-heavy-metals-in-apatite-mineral-4p7cddx7mm.pdf

Xiaobing Chen

Papers

Evaluation of heavy metal remediation using mineral apatite

In Situ Immobilization of Heavy Metals in Apatite Mineral Formulations

Ionic conduction mechanism in high concentration lithium ion electrolytes.

Dark repair of sunlight-inactivated tetracycline-resistant bacteria: Mechanisms and important role of bacteria in viable but non-culturable state.