Assessment of in situ immobilization of Lead (Pb) and Arsenic (As) in contaminated soils with phosphate and iron: solubility and bioaccessibility

The effect of in situ immobilization of lead (Pb) and arsenic (As) in soil with respectively phosphate and iron is well recognized. However, studies on combined Pb and As-contaminated soil are fewer, and assessment of the effectiveness of the immobilization on mobility and bioaccessibility is also necessary. In this study, a Pb and As-contaminated soil was collected from an abandoned lead/zinc mine in Shaoxing, Zhejiang province of China, which has been treated with three phosphates, i.e., calcium magnesium phosphate (CMP), phosphate rock, and single super-phosphate (SSP) for 6 months in a field study. The ferrous sulfate (FeSO4) at 20 g kg-1 was then amended to the soil samples and incubated for 8 weeks in a greenhouse. The solubility and bioaccessibility tests were used to assess the effectiveness of the in situ immobilization. The result showed that phosphates addition decreased the concentrations of CaCl2-extractable Pb; however, the concentrations of water-soluble As increased upon CMP and SSP addition. With the iron addition, the water-soluble As concentrations decreased significantly, but CaCl2-extractable Pb concentrations increased. The bioaccessibility of As and Pb measured in artificial gastric and small intestinal solutions decreased with phosphate and iron application except for the bioaccessibility of As in the gastric phase with SSP addition. Combined application of phosphates and iron can be an effective approach to lower bioaccessibility of As and Pb, but has opposing effects on mobility of As and Pb in contaminated soil

FeEDDHA-facilitated Fe uptake in relation to the behaviour of FeEDDHA components in the soil-plant system as a function of time and dosage.

FeEDDHA products are widely used to prevent and remedy Fe chlorosis in crops grown on calcareous soils. These products consist of a mixture of FeEDDHA components: racemic o,o-FeEDDHA, meso o,o-FeEDDHA, o,p-FeEDDHA and rest-FeEDDHA. The FeEDDHA components differ in physical and chemical properties, and as a consequence also in effectiveness as Fe fertilizer. In order to efficiently match dose, frequency and moment of FeEDDHA application with the Fe requirements of plants, it is important to understand the behaviour of the FeEDDHA components in the soil-plant system as a function of time and dosage, and to relate this behaviour to Fe uptake by plants. These issues have been examined in a pot trial study with soybean plants (Glycine max (L.) Merr. cv Mycogen 5072) grown on calcareous soil from Santomera, Spain. Four FeEDDHA treatments (two compositions, two dosages) were applied prior to the set in of chlorosis. Leaching of FeEDDHA components was prevented. Plant and soil were sampled every week, for six weeks. From one week onward the Fe concentration in the pore water was largely gouverned by racemic and meso o,o-FeEDDHA. The concentration behaviour of the o,o-FeEDDHA isomers underwent two stages: a strong decline within the first week resulting from linear adsorption, and a gradual decline from one week onward. For meso o,o-FeEDDHA, unlike racemic o,o-FeDDHA, the gradual decline could be mathematically well described with an exponential decay function. Soybean plants mainly took up Fe in the progressed vegetative stage (3rd and 4th week) and in the reproductive stage, when the pods were being filled with seeds (6th week). Fe uptake and removal of racemic o,o-FeEDDHA from the soil system display a similar time-trend, whereas the removal of meso o,o-FeEDDHA had a plant-independent character. This indicates the removal of racemic o,o-FeEDDHA is to a larger extent plant-relate

Inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

Acid–base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in principle does not require a molecular picture. The models are typically calibrated to relatively simple solid-electrolyte solution pairs and may provide poor descriptions of complex multi-component mineral–aqueous solutions, including those found in natural environments. Surface complexation models may be improved by incorporating molecular-scale surface structural information to constrain the modeling efforts. Here, we apply a concise, molecularly-constrained surface complexation model to a diverse suite of surface titration data for rutile and thereby begin to address the complexity of multi-component systems. Primary surface charging curves in NaCl, KCl, and RbCl electrolyte media were fit simultaneously using a charge distribution (CD) and multisite complexation (MUSIC) model [Hiemstra T. and Van Riemsdijk W. H. (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model. J. Colloid Interf. Sci. 179, 488–508], coupled with a Basic Stern layer description of the electric double layer. In addition, data for the specific interaction of Ca2+ and Sr2+ with rutile, in NaCl and RbCl media, were modeled. In recent developments, spectroscopy, quantum calculations, and molecular simulations have shown that electrolyte and divalent cations are principally adsorbed in various inner-sphere configurations on the rutile 1 1 0 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Predota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Bénézeth P., Anovitz L., Palmer D. A., Machesky M. L. and Wesolowski D. J. (2004) Ion adsorption at the rutile–water interface: linking molecular and macroscopic properties. Langmuir 20, 4954–4969]. Our CD modeling results are consistent with these adsorbed configurations provided adsorbed cation charge is allowed to be distributed between the surface (0-plane) and Stern plane (1-plane). Additionally, a complete description of our titration data required inclusion of outer-sphere binding, principally for Cl- which was common to all solutions, but also for Rb+ and K+. These outer-sphere species were treated as point charges positioned at the Stern layer, and hence determined the Stern layer capacitance value. The modeling results demonstrate that a multi-component suite of experimental data can be successfully rationalized within a CD and MUSIC model using a Stern-based description of the EDL. Furthermore, the fitted CD values of the various inner-sphere complexes of the mono- and divalent ions can be linked to the microscopic structure of the surface complexes and other data found by spectroscopy as well as molecular dynamics (MD). For the Na+ ion, the fitted CD value points to the presence of bidenate inner-sphere complexation as suggested by a recent MD study. Moreover, its MD dominance quantitatively agrees with the CD model prediction. For Rb+, the presence of a tetradentate complex, as found by spectroscopy, agreed well with the fitted CD and its predicted presence was quantitatively in very good agreement with the amount found by spectroscopy

FeEDDHA-facilitated Fe uptake in relation to the behaviour of FeEDDHA components in the soil-plant system as a function of time and dosage.

FeEDDHA products are widely used to prevent and remedy Fe chlorosis in crops grown on calcareous soils. These products consist of a mixture of FeEDDHA components: racemic o,o-FeEDDHA, meso o,o-FeEDDHA, o,p-FeEDDHA and rest-FeEDDHA. The FeEDDHA components differ in physical and chemical properties, and as a consequence also in effectiveness as Fe fertilizer. In order to efficiently match dose, frequency and moment of FeEDDHA application with the Fe requirements of plants, it is important to understand the behaviour of the FeEDDHA components in the soil-plant system as a function of time and dosage, and to relate this behaviour to Fe uptake by plants. These issues have been examined in a pot trial study with soybean plants (Glycine max (L.) Merr. cv Mycogen 5072) grown on calcareous soil from Santomera, Spain. Four FeEDDHA treatments (two compositions, two dosages) were applied prior to the set in of chlorosis. Leaching of FeEDDHA components was prevented. Plant and soil were sampled every week, for six weeks. From one week onward the Fe concentration in the pore water was largely gouverned by racemic and meso o,o-FeEDDHA. The concentration behaviour of the o,o-FeEDDHA isomers underwent two stages: a strong decline within the first week resulting from linear adsorption, and a gradual decline from one week onward. For meso o,o-FeEDDHA, unlike racemic o,o-FeDDHA, the gradual decline could be mathematically well described with an exponential decay function. Soybean plants mainly took up Fe in the progressed vegetative stage (3rd and 4th week) and in the reproductive stage, when the pods were being filled with seeds (6th week). Fe uptake and removal of racemic o,o-FeEDDHA from the soil system display a similar time-trend, whereas the removal of meso o,o-FeEDDHA had a plant-independent character. This indicates the removal of racemic o,o-FeEDDHA is to a larger extent plant-relate

Reaction mechanisms of phosphate with Al(OH)3 and a sandy soil

Al(OH) 3 is a very effective sorbent for orthophosphate especially at low pH. At low phosphate concentration c p , phosphate is adsorbed by an exchange mechanism with singly coordinated OH(H) groups residing on the surface of the Al(OH) 3 . In chapters 2 and 3 experiments are described using a well defined gibbsite (crystalline Al(OH) 3 ) as sorbent. A rate equation isselected that describes the adsorption reaction for a fractional coverage (amount adsorbed/maximum adsorption capacity) between 0.5 and 1.0. At intermediate and high c p values the sorption can easily exceed the maximum exchange-adsorptioncapacity. The maximum adsorption capacity of the gibbsite used was estimated with the help of shadowed electron micrographs. The sorption beyond the exchange adsorption maximum is identified as a precipitation process, i.e. it only occurs in supersaturated system . The rate of this precipitation reaction is shown to increase with increasing supersaturation and to decrease with in creasing amounts sorbed. Evidence is presented that indicates that the decrease of the reaction rate with increasing sorption is caused by the formation of coatings of a (K)-Al-phosphate on the gibbsite particles. The activation energy of this reaction is determined. The ratio of the OH that is produced during this sorption reaction and the phosphate sorption isfound to be independent of the extent of the reaction, for certain reaction conditions. A so called phosphato-stat (c p -stat) has been constructed that provides for both a constant pH and c p during the sorption reaction. The amount precipitated is found proportional with the square root of reaction time for the condition of constant supersaturation.The relative contribution of precitation and adsorption has been calculated as a function of c p and reaction time. It is furthermore shown that the nature and concentration of the accompanying cation has an effect on the precipitation rate (constant total electrolyte concentration).In chapter 4 experiments are described using X-ray amorphous Al(OH) 3 and αAl 2 O 3 as sorbent. A pure phosphate solution and a so called inorganic synthetic sewage water medium are used as electrolyte solution. There is sow effect of the electrolyte medium on the sorption rate as expected. The gene ral characteristics of the sorption reaction described in this chapter are similar to the results as found with gibbsite; in the initial stage of the reaction adsorption is the dominant reaction mechanism, whereas precipitation dominates the kinetics for longer reaction times.In chapter 5 experiments are described that make use of columns either filled with quartz sand or quartz sand mixed with X-ray amorphous Al(OH) 3 . Raw domestic sewage water (pH ≈8) was added to the columns once every two weeks during 10 months. It is shown that the sorption of phosphate from sewage water in the Al-containing column is higher than would be expected from pure inorganic system experiments. Evidence is presented that indicates that a CaAl-phospate has been formed in the Al-containing sand column (Ca was absent in the pure system experiments to prevent the complication of the formation of calciumphosphates). The quartz sand columns acted as a sieve for solid compnents of the sewage water only.Experiments using an acid sandy soil with a low organic matter content as sorbent for phosphate are described in chapter 6. The main characteristics of the sorption reaction as determined from the experiments using Al(OH) 3 were also found in the sorption experiments using this soil. Use has been made of the phosphato-stat to provide conditions of constant supersaturation during the reaction. It is shown beyond doubt that the reaction rate continuously decreases at constant supersaturation as the reaction proceeds. The components of the soil that are active in the phosphate sorption process are most probably the (amorphous) aluminum-iron-oxides-hydroxides of the soil. The amount of extractable iron and aluminum was determined.The mechanism of the phosphate sorption reaction using metal oxides as sorbent is compared with the oxidation mechanism of metals.The phosphato-stat method may be used in combination with a (micro) computer, facilitating the collection of phosphate sorption rate data on a somewhat larger scale for practical applications.<p/

Humic acid protein complexation

Interactions of purified Aldrich humic acid (PAHA) with lysozyme (LSZ) are investigated. In solution LSZ is moderately positively and PAHA negatively charged at the investigated pH values. The proton binding of PAHA and of LSZ is determined by potentiometric proton titrations at various KCl concentrations. It is also measured for two mixtures of PAHA¿LSZ and compared with theoretically calculated proton binding assuming no mutual interaction. The charge adaptation due to PAHA¿LSZ interaction is relatively small and only significant at low and high pH. Next to the proton binding, the mass ratio PAHA/LSZ at the iso-electric point (IEP) of the complex at given solution conditions is measured together with the pH using the Mütek particle charge detector. From the pH changes the charge adaptation due to the interaction can be found. Also these measurements show that the net charge adaptation is weak for PAHA¿LSZ complexes at their IEP. PAHA/LSZ mass ratios in the complexes at the IEP are measured at pH 5 and 7. At pH 5 and 50 mmol/L KCl the charge of the complex is compensated for 30¿40% by K+; at pH 7, where LSZ has a rather low positive charge, this is 45¿55%. At pH 5 and 5 mmol/L KCl the PAHA/LSZ mass ratio at the IEP of the complex depends on the order of addition. When LSZ is added to PAHA about 25% K+ is included in the complex, but no K+ is incorporated when PAHA is added to LSZ. The flocculation behavior of the complexes is also different. After LSZ addition to PAHA slow precipitation occurs (6¿24 h) in the IEP, but after addition of PAHA to LSZ no precipitation can be seen after 12 h. Clearly, PAHA/LSZ complexation and the colloidal stability of PAHA¿LSZ aggregates depend on the order of addition. Some implications of the observed behavior are discussed