Effect of adsorbed metal ions on the transport of Zn- and Ni-EDTA complexes in a sand and gravel aquifer

Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales.     

Cadmium adsorption on hydrous aluminium (III) oxide: effect of adsorbed polyelectrolyte

Freshly precipitated hydrous oxides of Al (flocs) are important sorbents of heavy metal ions and are used in water treatment processes. The addition of chelating agents or polyelectrolytes can increase the efficiency of heavy metal removal by flocs. The polymer polyethylenimine is commonly used as a flocculant aid in water treatment and has been modified with phthalic acid. Adsorption studies have shown that the addition of millimolar concentrations of polyelectrolyte increases the removal of Cd ions from a 29.7 μM aqueous solution by aluminium flocs from ca. 40% to up to 75%. Experiments in which the pH was varied demonstrated that the observed enhancement of Cd adsorption is caused by a shift of the pH edge to lower pH values in the presence of polyelectrolyte. Maximum polyelectrolyte adsorption occurs between pH 6 and pH 7, corresponding to the point of enhanced Cd adsorption in the presence of polyelectrolyte. The enhancement of Cd adsorption observed below pH 7 is therefore likely to be due to the formation of a ternary surface complex. At pH values above pH 8 the polyelectrolyte forms a stable complex with Cd and Al ions in solution causing floc dissolution and decreased Cd adsorption.     

The oxidation of pyrite at pH 7 in the presence of reducing and nonreducing Fe(III)-chelators

The oxidation rate of pyrite at pH 7, 25°C and at constant partial pressure of oxygen (0.21 and 0.177 atm) was measured in the presence of the Fe(III)-chelators NTA, oxalate, leucine, EDTA, citrate, IDA and the Fe(III)-reductant ascorbic acid. With the exception of leucine and EDTA, non-reducing Fe(III)-chelators increased the oxidation rate relative to the reference state of formation of the Fe(OH)₂⁺ complex at pH 7. The rate increase was proportional to the logarithm of the conditional stability constant of the ligands for the complexation of Fe³⁺. No effect on the oxidation rate was observed in the presence of EDTA, which shifted the redox potential of the redox couple Fe²⁺/Fe³⁺ to a value below that in the absence of any ligand at pH 7. Ascorbic acid decreased the pyrite oxidation rate by a factor of 5 at ascorbic acid concentrations between 10⁻⁴ and 10⁻² mol L⁻¹. Comparison of the rate constants for the oxidation of ascorbic acid by surface bound Fe(III) in the absence and presence of pyrite shows that the pyrite surface accelerates this reaction by a factor of 10. The oxidation of both pyrite and ascorbic acid is of fractional order with respect to ascorbic acid (HAsc): r_py=0.55 c(HAsc)^−0.35 r_HAsc=3.6 c(HAsc)^0.59. Both the results from experiments with Fe(III)-chelating ligands and the Fe(III)-reductant, suggest a very efficient interference in the electron cycling between Fe(II) and Fe(III) at the pyrite surface. The interference seems to be mainly related to the reductive side of the iron cycling. It is therefore concluded that the electron transfer between ferric iron and pyritic sulfur limits the pyrite oxidation rate at pH 7.     

Siderophore adsorption to and dissolution of kaolinite at pH 3 to 7 and 22°C

Siderophores are Fe(III)-specific ligands produced by many aerobic microorganisms under conditions of iron stress. This study examined adsorption of the commercial trihydroxamate siderophore, desferrioxamine B (DFO-B), to an iron-containing kaolinite (0.1 bulk wt.% Fe) and examined DFO-B effects on initial kaolinite dissolution and iron release rates. Adsorption experiments were conducted at pH 3 to 8 in 0.01-M NaClO₄ in the dark and at 22°C; batch initial dissolution experiments were conducted to 96 h.The adsorption envelope (i.e., adsorption as a function of pH) of DFO-B on kaolinite was consistent with cation-like behavior, with adsorption increasing above kaolinite’s pH_pznpc of 4.9. DFO-B enhanced aluminum release from kaolinite at pH 3 to 7, relative to HNO₃, which is consistent with the ligand’s high binding affinity for Al. Correlation between DFO-B adsorption and aluminum release suggested a surface-controlled, ligand-promoted dissolution mechanism. DFO-B had no effect relative to HNO₃ on silicon release at pH 3 and 5, but moderately enhanced silicon release at pH 7. DFO-B enhanced iron release from kaolinite, with dissolved iron concentrations in the 10-ppb range at 96-h reaction time. These results show that kaolinite may serve as a source of iron to aerobic microorganisms in iron-limited conditions and that siderophores may affect kaolinite dissolution and iron content.     

镉及其络合物在黏土上的吸附行为

淋洗剂EDTA 二钠和柠檬酸三钠与镉形成的络合物及镉本身在黏土上的吸附行为研究表明: 上述两种淋洗剂能有效提取表层土中的Cd,形成的络合物在迁移过程中又能较好地被黏土层吸附。黏土对Cd2 +、Cd--EDTA 和Cd--柠檬酸的吸附容量顺序为: Cd--柠檬酸＞ Cd2 + ＞ Cd － EDTA; 3 种形态的吸附过程均以离子交换吸附为主,并在15 min 内完成。黏土对Cd2 + 和Cd － 柠檬酸的吸附容量随溶液初始pH 的升高而增大,对Cd--EDTA 的吸附容量随pH 升高略有降低。     

Adsorption of hydroxamate siderophores and EDTA on goethite in the presence of the surfactant sodium dodecyl sulfate

Siderophore-promoted iron acquisition by microorganisms usually occurs in the presence of other organic molecules, including biosurfactants. We have investigated the influence of the anionic surfactant sodium dodecyl sulfate (SDS) on the adsorption of the siderophores DFOB (cationic) and DFOD (neutral) and the ligand EDTA (anionic) onto goethite (α-FeOOH) at pH 6. We also studied the adsorption of the corresponding 1:1 Fe(III)-ligand complexes, which are products of the dissolution process. Adsorption of the two free siderophores increased in a similar fashion with increasing SDS concentration, despite their difference in molecule charge. In contrast, SDS had little effect on the adsorption of EDTA. Adsorption of the Fe-DFOB and Fe-DFOD complexes also increased with increasing SDS concentrations, while adsorption of Fe-EDTA decreased. Our results suggest that hydrophobic interactions between adsorbed surfactants and siderophores are more important than electrostatic interactions. However, for strongly hydrophilic molecules, such as EDTA and its iron complex, the influence of SDS on their adsorption seems to depend on their tendency to form inner-sphere or outer-sphere surface complexes. Our results demonstrate that surfactants have a strong influence on the adsorption of siderophores to Fe oxides, which has important implications for siderophore-promoted dissolution of iron oxides and biological iron acquisition.     

Aerobic oxidation of mackinawite (FeS) and its environmental implication for arsenic mobilization

Oxidation of mackinawite (FeS) and concurrent mobilization of arsenic were investigated as a function of pH under oxidizing conditions. At acidic pH, FeS oxidation is mainly initiated by the proton-promoted dissolution, which results in the release of Fe(II) and sulfide in the solution. While most of dissolved sulfide is volatilized before being oxidized, dissolved Fe(II) is oxidized into green rust-like precipitates and goethite (α-FeOOH). At basic pH, the development of Fe(III) (oxyhydr)oxide coating on the FeS surface inhibits the solution-phase oxidation following FeS dissolution. Instead, FeS is mostly oxidized into lepidocrocite (γ-FeOOH) via the surface-mediated oxidation without dissolution. At neutral pH, FeS is oxidized via both the solution-phase oxidation following FeS dissolution and the surface-mediated oxidation mechanisms. The mobilization of arsenic during FeS oxidation is strongly affected by FeS oxidation mechanisms. At acidic pH (and to some extent at neutral pH), the rapid FeS dissolution and the slow precipitation of Fe (oxyhydr)oxides results in arsenic accumulation in water. In contrast, the surface-mediated oxidation of FeS at basic pH leads to the direct formation of Fe (oxyhydr)oxides, which provides effective adsorbents for As under oxic conditions. At acidic and neutral pH, the solution-phase oxidation of dissolved Fe(II) accelerates the oxidation of the less adsorbing As(III) to the more adsorbing As(V). This study reveals that the oxidative mobilization of As may be a significant pathway for arsenic enrichment of porewaters in sulfidic sediments.     

Relationships Between Geochemical Parameters (pH, DOC, SPM, EDTA Concentrations) and Trace Metal (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn) Concentrations in River Waters of Texas (USA)

Water samples from eight major Texas rivers were collected at different times during 1997–1998 to determine the dissolved and particulate trace metal concentrations, expected to show differences in climate patterns, river discharge and other hydrochemical conditions, and human activities along the different rivers. Specifically, two eastern Texas rivers (Sabine, Neches) lie in a region with high vegetation, flat topography, and high rainfall rates, while four Central Texas rivers (Trinity, Brazos, Colorado, and San Antonio) flow through large population centers. Relatively high dissolved organic carbon (DOC) concentrations in the eastern Texas rivers and lower pH led to higher Fe and Mn concentrations in river waters. The rivers that flow through large population centers showed elevated trace metal (e.g., Cd, Pb, Zn) concentrations partly due to anthropogenically produced organic ligands such as ethylenediaminetetraacetic acid (EDTA) present in these rivers. Trace metal levels were reduced below dams/reservoirs along several Texas rivers. Statistical analysis revealed four major factors (suspended particulate matter [SPM], EDTA, pH, and DOC) that can explain most of the observed variability of trace metal concentrations in these rivers. SPM concentrations directly controlled particulate metal contents. Variation in pH correlated with changes of dissolved Co, Fe, Mn, and Ni, and particulate Mn concentrations, while DOC concentrations were significantly related to dissolved Fe concentrations. Most importantly, it was found that, more than pH, EDTA concentrations exerted a major control on dissolved concentrations of Cd and Zn, and, to a lesser extent, Cu, Ni, and Pb.     

The coagulation,solubility and adsorption properties of Fe,Mn, Cu,Ni, Cd,Co and humic acids in a river water

River water (Water of Luce, Scotland) is used in laboratory experiments designed to investigate physical and chemical properties of Fe. Mn, Cu, Ni, Co, Cd and humic acids in riverine and estuarine systems. Using NaCl, MgCl₂ and CaCl₂ as coagulating agents, coagulation of dissolved (0.4 μm filtered) Fe, Cu, Ni, Cd and humic acids increases in a similar matter with increasing salt molarily: Ca²⁺ is the most dominant coagulating agent. Removal by coagulation with Ca²⁺ at seawater concentrations ranges from large (Fe-80%. HA-60%, Cu-40%) to small (Ni, Cd-15%) to essentially nothing (Cd, Mn-3%). Destabilization of colloids is the indicated mechanism. Solubility-pH measurements show that between a pH of 3 and 9, Fe, Cu, Ni, Mn, Co and Cd are being held in the dissolved phase by naturally occurring organic substances. Between pH of 2.2 and 1.2 a large proportion of dissolved Fe, Cu. Ni and Cd (72, 35,44 and 36% respectively) is precipitated along with the humic acids; in contrast, Mn and Co show little precipitation (3%). Adsorption-pH experiments, using unfiltered river water spiked with Cu, indicate that adsorption of Cu onto suspended particles is inhibited to a large extent by the formation of dissolved Cu-organic complexes.The experimental results demonstrate that solubilities and adsorption properties of certain trace metals in freshwaters can be opposite to those observed with artificial solutions or predicted with chemical models. Interaction with organic substances is a critical factor.     

Effects of aqueous complexation on reductive precipitation of uranium by Shewanella putrefaciens

We have examined the effects of aqueous complexation on rates of dissimilatory reductive precipitation of uranium by Shewanella putrefaciens. Uranium(VI) was supplied as sole terminal electron acceptor to Shewanella putrefaciens (strain 200R) in defined laboratory media under strictly anaerobic conditions. Media were amended with different multidentate organic acids, and experiments were performed at different U(VI) and ligand concentrations. Organic acids used as complexing agents were oxalic, malonic, succinic, glutaric, adipic, pimelic, maleic, citric, and nitrilotriacetic acids, tiron, EDTA, and Aldrich humic acid. Reductive precipitation of U(VI), resulting in removal of insoluble amorphous UO₂ from solution, was measured as a function of time by determination of total dissolved U. Reductive precipitation was measured, rather than net U(VI) reduction to U(IV), to assess overall U removal rates from solution, which may be used to gauge the influence of chelation on microbial U mineralization. Initial linear rates of U reductive precipitation were found to correlate with stability constants of 1:1 aqueous U(VI):ligand and U(IV):ligand complexes. In the presence of strongly complexing ligands (e.g., NTA, Tiron, EDTA), UO₂ precipitation did not occur. Our results are consistent with ligand-retarded precipitation of UO₂, which is analogous to ligand-assisted solid phase dissolution but in reverse: ligand exchange with the U⁴⁺ aquo cation acts as a rate-limiting reaction moderating coordination of water molecules with U⁴⁺, which is a necessary step in UO₂ precipitation. Ligand exchange kinetics governing dissociation rates of ligands from U(VI)-organic complexes may also influence overall UO₂ production rates, although the magnitude of this effect is unclear relative to the effects of U(IV)-organic complexation. Our results indicate that natural microbial-aqueous systems containing abundant organic matter can inhibit the formation of biogenic amorphous UO₂.     

Chelate-assisted phytoextraction of cadmium from a mine soil by negatively charged sunflower

The effects of some chelating agents and electricity on cadmium phytoextraction from a mine soil were examined in pot culture of sunflower to achieve more remediation efficiency. At the beginning of the flowering stage, ethylene-diamine-tetra-acetic acid (EDTA) as a chemical chelator, cow manure extract (CME) and poultry manure extract (PME) as organic chelators were applied (2 g kg^?1 soil) during irrigation. Seven days later, Helianthus annuus was negatively charged by inserting a stainless steel needle in the lowest part of the stem with 10 and 30 V direct current electricity for 1 h each day for 14 days. Afterward, concentration of cadmium in roots and shoots, cadmium translocation factor (TF), cadmium uptake index (UI) and soil available (diethylene-triamine-penta-acetic acid extractable) cadmium were measured. Results indicated that EDTA reduced roots dry weight while none of the roots and shoots was affected by other chelating agents and by electrical treatment as well. Highest concentration of cadmium in shoots was measured in 10 V-control with no significant differences with 30 V-PME and 30 V-EDTA. Utilization of chelating agents did not increase the cadmium TF and cadmium UI while highest values for cadmium TF and cadmium UI were observed in 10 and 30 V treatments, respectively. Available cadmium in the soil near root system treated with 10 and 30 V was relatively lower compared with the soil far from root system. Results of this experiment indicated that charging the plant with direct current electricity ameliorated the efficiency of cadmium phytoremediation.     

Pressure-assisted cyclic washing of heavy-metal-contaminated sediments

Remediation of heavy-metal-contaminated sediment is often hampered by the availability of heavy metals to the added chemical agents because the heavy metals are often shielded by the sediment matrix. Effective heavy-metal extraction technique becomes an important factor in enhancing the treatment efficiency. A novel extraction/washing technique utilizing chelating agent and elevated pressure in consecutive cycles of compression and decompression has been developed for heavy-metal-contaminated sediment washing in the presence of chelating agent. In this study, the optimal operational conditions of pressure-assisted cyclic washing of Cu-contaminated sediments (initial Cu concentration = 23.177 mg/kg) were determined in a laboratory-scale system. The control factors included applied pressure level, washing time, applied chelant [ethylenediamine-tertraacetic (EDTA)] concentration (0.01–0.5 M), pressure times, and application of consecutive batches washing. Results from the bench-scale study showed that up to 70 % of Cu can be removed from the sediments when 10 atm of pressure was applied for washing. The efficiency dropped to 55 % when the pressure dropped to 6 atm. Under the same operational conditions, the optimal cyclic washing time was 60 min. Results from the particle size analyses indicate that the mean particle size dropped from 100 to 50 μm after the pressure-assisted cyclic washing. Thus, cyclic pressure caused the fracture of sediment aggregates resulting in the exposure of Cu to chelating agents. With the assistance of pressure cyclic system, the total washing time and the amount of added chemical agent used can be significantly reduced.     

The mechanism and kinetics of DTPA-promoted dissolution of barite

The dissolution rate of natural barite, BaSO₄, was measured in solutions of DTPA (diethylene triamine penta-acetic acid) to investigate the mechanism of ligand-promoted dissolution using a strong chelating agent. Experiments were carried out over a range of DTPA concentrations 0.5–0.0001 M solutions, at room temperature (22 °C), as well as a range of temperatures, 22–80 °C at 1 atm. The dissolution rate is inversely related to the DTPA concentration in solution. A more dilute DTPA solution is shown to be more efficient as a solvent in terms of the approach to the equilibrium saturation value for the dissolution of Ba²⁺. An analysis of the temperature dependence of the dissolution rate at high pH by the determination of activation energies indicates that the reaction is probably controlled by the pre-exponential term in the rate constant. This indicates that reaction frequency mostly controls differences in reactivity and suggests an explanation for the results in terms of stearic hindrance due to adsorbed DTPA molecules at the barite surface. The effect of DTPA on the solvation of the Ba²⁺ ion may also influence the dissolution rate.     

Dissolution of secondary copper sulphides using complex-forming agents (EDTA,EDA). Part I: Covellite dissolution in EDTA and EDA

Problems of dissolution of the so-called secondary copper sulphides are very important for dynamic as well as percolation leaching of ores. This paper deals with dissolution kinetics of sulphides in an alkaline medium, using complex-forming agents in connection with possibility to leach basic, partially oxidized ores. Natural minerals and their polydispersions were investigated and the so-called geometrical model was used for evaluation. Basic dependences of the dissolution rate on the reagent concentration and pH value of the leaching solution were found and an attempt at their mathematical expression and physical interpretation was made. The first part of this work refers to the systems of covellite-ethylene diamine tetra-acetic acid (EDTA) and covellite-ethylene diamine (EDA). The established dependences are not only of theoretical but also of practical importance.     

Efficiency of chelating agents in retaining sludge-borne heavy metals in intensively applied agricultural soils

This paper presents an evaluation of different chelating agents for their effectiveness in removing Cu, Co and Zn in three distinctly different types of sludge-amended soils. Soil types (Luvisol, Arenosol and Vertisol) were each mixed with an anaerobically digested sludge at a 1:1 ratio followed by leaching with three types of chelating agents, namely: ethylenediamine tetra acetic acid, nitrilotriacetic acid and acetic acid. Aqua regia method was used to quantify pseudo total metal before and after treatment. Generally, chelating agents can be out competed by soil colloids in attracting cations. The efficiency of chelating agents was found to follow this order ethylenediamine tetra acetic acid?<?nitrilotriacetic?=?acetic acid in all the three metals, with ethylenediamine tetra acetic acid being the most effective chelating agent. More heavy metals were removed in Luvisol and Arenosol than in Vertisol implying that soils rich in clay fraction retain more cations than soils with minimal clay fraction. Similarly, copper responded positively to chelation than zinc and cobalt in Luvisols and Arenosols, although the results were not conclusive for Vertisols.     

Reclamation of EDTA by sodium tetraethylenepentamine-multi dithiocarbamate after soil washing process with EDTA

Ethylenediaminetetraaceticacid (EDTA) has been proven to be an efficient soil washing liquid to remove metal contaminants from soils. However, EDTA may cause secondary pollution due to its low biodegradability if it is not recycled or destroyed in the washing process. Thus, it is necessary to recycle and recover EDTA for sustainable use. In this paper, the extracting performance of fresh EDTA was firstly studied as a function of EDTA concentration, liquid/sediment (L/S) ratio and pH of the solution, and also extraction time. Then sodium tetraethylenepentamine-multi dithiocarbamate (TEPA-DTC), a heavy metals capturing agent, was synthesized on the base of the research of LIU-Lihua. Compared with Na₂S and DDTC, TEPA-DTC shows strong chelating capacity, because it has functional groups of dithiocarbamate that could strongly chelate heavy metals and capture metal ions from Me-EDTA to form precipitates, allowing us to reclaim the EDTA during the process of soil washing. Three divalent heavy metals were investigated (Pb, Cd, and Cu). These three metals could almost precipitate completely with TEPA-DTC under the dosage of 300 mg/l, and EDTA was regenerated. The recovered EDTA was used again in three cycles of soil washing, and the amount of heavy metals extracted just slightly decreased each cycle.     

Sulfide mineral oxidation in freshly processed tailings: batch experiments

This work focuses on sulfide mineral oxidation rates under oxic conditions in freshly processed pyrite-rich tailings from the ore concentrator in Boliden, northern Sweden. Freshly processed tailings are chemically treated in the plant to kill bacteria and to obtain increased metal yields, resulting in a high pH level of 10–12 in the process water. Different oxidation experiments (abiotic oxidation in untreated tailings, acid abiotic oxidation and acid microbial oxidation), containing the Boliden tailings, were performed at room temperature with dissolved oxygen (0.21 atm O₂) for 3 months. The different pyrite oxidation rates given from the study were 2.4×10⁻¹⁰ mol m⁻² s⁻¹ for the microbial, 5.9×10⁻¹¹ mol m⁻² s⁻¹ for the acidic abiotic and 3.6×10⁻¹¹ mol m⁻² s⁻¹ for the untreated experiments. Because of the potential precipitation of gypsum in the batch solutions, these oxidation rates are considered minimum values. The release rates for copper and zinc from chalcopyrite and sphalerite in the acid experiments were also investigated. These rates were normalized to the metal concentration in the tailings, and then compared to the release rate for iron from pyrite. These normalized results indicated that metal release decreased in the order Cu>Zn>Fe, demonstrating that pyrite is more resistant to oxidation than sphalerite and chalcopyrite. Pyrite was also more resistant to acidic dissolution than to microbial dissolution, while a significant fraction of sphalerite and chalcopyrite dissolved in the acid abiotic solutions.     

Dissolution Characteristic Study on Dustfall in Citric

In this paper, the dissolution characteristics of Xining dustfall in citric acid solution was studied to evaluate the physical chemical change in acid conditions. pH along with conductivity was tested with time. FTIR, SEM and ICP analysis were applied to analyze the residuum and filtrate after 2 days’ dissolution experiment. It was shown in the pH/conductivity variation, solution’s pH rise sharply in the front 4 hours, then decrease slowly. After 4 hours, both the pH and conductivity become stable. Based on combined analysis of XRD and FTIR spectrum of dustfall before and after dissolution, that calcite and dolomite in dustfall are dissolved completely in the 0.05M citric acid solution in two days. Besides, amount of metal cations were extracted from the dustfall during the dissolution, including Ca2+,K+,Mg2+,Fe3+,Al3+,Si. In general, after the dissolution of dustall in citric acid, some minerals are dissolved and amount of metal elements are extracted. Carbonate minerals almost dissolved completely, also the structure of silicate minerals changed as the extraction of elements.     

Experimental study of igneous and sedimentary apatite dissolution: Control of pH, distance from equilibrium, and temperature on dissolution rates

Apatite dissolution experiments were conducted using both a fluidized bed and stirred tank reactor over a range of pH, temperature, solution saturation state, and on non-carbonated and carbonated apatite compositions: igneous fluorapatite (FAP) and sedimentary carbonate fluorapatite (CFA), respectively. From 2 <pH <6, the rate of release from dissolution of all apatite components [calcium (Ca), phosphorus (P), and fluoride (F)] increased with decreasing pH for FAP. From 6 < pH < 8.5, the FAP dissolution rate is pH independent. Measuring apatite dissolution rates at pH > 8.5 were not possible due to detection limits of the analytical techniques used in this study and the high insolubility of FAP. For the CFA compositions studied, the dissolution rate decreased with increasing pH from 4 < pH < 7. During early stages of the dissolution reaction for both FAP and CFA, mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P and Ca:F being greater than mineral stoichiometric ratios, suggesting that Ca was preferentially released compared to P and F from the mineral structure during the early stages of dissolution. An increase in reacted solution pH accompanies this early elevated release of Ca. As the dissolution reaction proceeded to steady state, dissolution became congruent. When normalized to BET measured surface area, FAP dissolved faster from 4 < pH < 7 compared to CFA. The apparent Arrhenius activation energy (E_a) of FAP dissolution over the temperature range of 25-55°C at pH = 3.0, I = 0.1, and pCO₂ = 0 is 8.3 ± 0.2 kcal mol⁻¹. Both the apparent exchange of solution H⁺ for solid-bound Ca at low pH in the early stage of dissolution and the E_a of dissolution suggest a surface and not a diffusion controlled dissolution reaction for FAP and CFA. The degree of undersaturation of the solution, ΔG_R, with respect to FAP was important in determining the dissolution rate. At pH = 3.0, I = 0.1, and pCO₂ = 0, the dissolution rate of FAP was ∼ 5× greater in the far-from-equilibrium region compared to the near-equilibrium slope region.A simple apatite weathering model incorporating the experimental results from this study was constructed, and numerical calculations suggest that during the Phanerozoic both the surface area of igneous rock available for weathering and the average global temperature were important factors in determining the P weathering flux from apatite dissolution. It is possible that elevated global temperatures coupled with relatively high surface area of igneous rock during the early- to mid-Paleozoic resulted in elevated P weathering fluxes, which along with climatic evolutionary pressures of the Neoproterozoic, facilitated the radiation of multicellular organisms, large-scale phosphorite deposition, and abundance of calcium phosphate shelled organisms during the early Cambrian.     

Experimental mobilization of metals from aquatic sediments by nitrilotriacetic acid

Nitrilotriacetic acid (NTA) and other synthetic complexing agents have recently come into use as partial substitutes for polyphosphates in detergents. Large amounts of heavy metals are solubilized (“complexed”) when highly polluted river sediments are treated with solutions containing NTA. This could endanger the drinking-water supplies in areas using river and lake water.Our experiments with polluted river sediments (NTA concentrations 1–100 ppm; shaking time 10–200 hours) indicate a high percentage mobilization of heavy metals with copper, cadmium and — to a lesser extent — nickel showing a positive correlation with both concentration of NTA and time of shaking.The release of zinc and lead is positively correlated with NTA concentration but shows a negative correlation with time of shaking — possibly due to the biodegradation of the (less stable) Pb and Zn chelates. With chromium no mobilization at any concentration or with any time of shaking could be observed.