Effect of acid deposition on the displacement of Al(III) in soils

This study represents an assessment of some of the key factors influencing the mobility of Al(III) and its displacement in acid soils. This assessment is based on the effect of pH and other solution variables on the solubility of Al(III) and its complex formation with OH^?, F^? and organic ligands (fulvates and humates). Above all, the adsorption behavior of Al(III) on iron(III) (hydr)oxides and on SiO₂ on one hand, and the adsorption of organic acids and of humic substances on mineral surfaces on the other hand was investigated. Adsorption is interpreted in terms of surface complex formation equilibria; the mass law constants derived permit the modeling of adsorption as a function of solution variables. It is illustrated that the distribution of oxides and hydroxides in the soil profile affects the pH buffering, determines the mobility of the organic acids while the mobility of Al(III) is primarily governed by the formation and dissolution of Al(III) (hydr)oxides.     

Mechanisms controlling the mobility of dissolved organic matter, aluminium and iron in podzol B horizons

The processes governing the (im)mobilization of Al, Fe and dissolved organic matter (DOM) in podzols are still subject to debate. In this study we investigated the mechanisms of (im)mobilization of Al, Fe and organic matter in the upper and lower B horizons of two podzols from the Netherlands that are in different stages of development. We equilibrated batches of soil material from each horizon with DOM solutions obtained from the Oh horizon of the corresponding soil profiles. We determined the amount of (im)mobilized Al, Fe and DOM after addition of Al and Fe at pH 4.0 and 4.5 and initial dissolved organic carbon (DOC) concentrations of 10 mg C litre^?1 or 30 mg C litre^?1, respectively. At the combination of pH and DOC concentrations most realistic for the field situation, organic matter was retained in all horizons, the most being retained in the lower B horizon of the well‐developed soil and the least in the upper B horizon of the younger profile. Organic matter solubility seemed to be controlled mainly by precipitation as organo‐metal complexes and/or by adsorption on freshly precipitated solid Al‐ and Fe‐phases. In the lower B horizons, at pH 4.5, solubility of Al and Fe appeared to be controlled mainly by the equilibrium with secondary solid Al‐ and Fe‐phases. In the upper B horizons, the solubility of Al was controlled by adsorption processes, while Fe still precipitated as inorganic complexes as well as organic complexes in spite of the prevailing more acidic pH. Combined with a previous study of eluvial horizons from the same profiles, the results confirm the important role of organic matter in the transport of Al and Fe to create illuvial B horizons initially and subsequently deepening and differentiating them into Bh and Bs horizons.     

Aluminum status of synthetic Al–humic substance complexes and their influence on plant root growth

Abstract

Aluminum (Al)–humus complexes are abundant in the A horizons of non-allophanic Andosols and contribute to the unique properties of volcanic ash soils, such as high reactivity with phosphate ions and a low bulk density. Natural non-allophanic Andosols commonly show Al toxicity to plant roots. There have been very few studies examining the contribution of Al–humus complexes to the Al toxicity of plant roots, although the complexes are the probable source of the toxic Al. We extracted humic substances from the A horizon of a non-allophanic Andosol using NaOH solution and reacted the humic substances and partially neutralized the AlCl₃ solution at three pH conditions (pH 4.0, 4.5 and 5.5) to prepare pure Al–humic substance complexes. The Al solubility study (equilibrium study in 10^?2 mol L^?1 CaCl₂) and the Al release study (a stirred-flow method using 10^?3 mol L^?1 acetate buffer solution adjusted to pH 3.5) indicated that all the synthetic complexes easily and rapidly release monomeric Al into the liquid phase with slight changes in pH and ion strength, although the Al contents and their extent of polymerization are considerably different among the complexes. A plant growth test was conducted using a medium containing the Al–humic substance complexes and perlite mixture. Root growth in burdock (Arctium lappa) and barley (Hordeum vulgare L.) was reduced equally by all three complex media, and the roots showed the typical injury symptoms of Al toxicity. These results indicate that in soils dominated by Al–humus complexes the Al released from the Al–humus complexes, as well as the exchangeable Al adsorbed by soil minerals, is definitely toxic to plant roots.     

Effect of Low Molecular Weight Organic Anions on Adsorption of Aluminum by Variable Charge Soils

To examine the effect of organic anions on adsorption of Al by variable charge soils at different pH values, the adsorption by three soils in the presence of three low-molecular-weight aliphatic carboxylic acids was investigated. The results showed that the effect depended on pH, the type of organic anions and their concentration. The presence of citrate and oxalate led to an increase in the adsorption of Al at low pH and low concentration of organic anions, with citrate showing a stronger effect than oxalate. For example, the maximum increments of Al adsorption in the presence of citrate were 131.9, 104.8 and 32.9% in the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively, whereas in the presence of oxalate it was 36.1% in the Rhodic Ferralsol. At high pH or high concentration of organic anions, they showed an inhibiting effect on the adsorption of Al. For example, citrate caused the increase in Al adsorption by 164.0, 131.0 and 61.0% at pH3.85 and the decrease in Al adsorption by 15.2, 19.5 and 45.6% at pH 4.8 for the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively. In the citrate and oxalate systems, the adsorption of Al increased with the increase in the concentration of organic anions, reaching a maximum values at about 0.4 mmol L^?1, and then decreased. When the concentration of organic anions was higher than about 1.0 mmol L^?1, both citrate and oxalate inhibited the adsorption of Al. The ability of organic anions in increasing the adsorption at low pH and decreasing the adsorption at high pH followed the same order: citrate > oxalate > acetate. The increase of Al adsorption at low pH is caused by the increase in soil negative surface charge as a result of the adsorption of organic anions by variable charge soils, while the decrease of Al adsorption at high pH and high concentration of organic anions is related to the competition of organic ligands for aluminum ions with soil surface. After the removal of free iron oxides from the soil, Al adsorption decreased in the presence of citrate, the anion species most strongly adsorbed by variable charge soils and complexed with aluminum ions. For example, for the Rhodic Ferralsol and the Ferric Acrisol, the removal of free iron oxides caused a decrease in the adsorption of Al in the presence of citrate at pH4.4 by 26.2 and 21.9%, respectively.     

Soil podzolization induced by reforestation as shown by sequential and kinetic extractions of Fe and Al

The impact of 60‐year‐old reforestation on soil evolution was studied by following the evolution of Fe and Al distribution as an indicator of early podzolization. We determined the distribution of Al and Fe in soils by combining sequential and kinetic extractions. We extracted the soil sequentially with: 1 mol litre^?1 sodium acetate at pH 5.5 (stage 1); twice with 0.1 mol litre^?1 sodium pyrophosphate at pH 10 (stage 2 and 2b); and with 1 mol litre^?1 hydroxylamine in 4.3 mol litre^?1 acetic acid solution at 90°C (stage 3). For each, we drew a kinetic‐extraction curve. We show that no re‐adsorption, precipitation or complexation with dissolved organic matter occurred for the reaction times recommended in this procedure, that is 6 hours for stage 1, 1.5 hours for stage 2 and 2b and 3 hours for stage 3. For a given extraction, the kinetic curves have the same shape for all samples, that is their behaviour is similar for a given reagent. Sequential extraction can therefore be used to compare the speciation of metals in different samples taken from the same soil. In addition, 60 years after reforestation by beech, a decrease of 12 and 17% is noted in the total Fe and Al contents, respectively, in the 0–10 cm layer, accompanied by a re‐distribution of these elements within the different soil compartments: a decrease of the Fe and Al bound to oxy‐hydroxide in favour of organic complexes and more soluble forms. Sequential extraction is therefore a good indicator of the first pedogenetic modifications induced by human intervention through reforestation.     

Phosphate,Fe and Mn uptake of N2 fixing red clover and ryegrass from an Oxisol as affected by P and model humic substances application. 1. Plant parameters and soil solution composition

The effect of humic substances on P-availability in soil is still debated. Therefore, the effect of model humic substances synthesized from hydroquinone on P, Fe, and Al solubility in a strong P fixing Oxisol and on P acquisition by red clover and ryegrass was investigated. After 4 months of incubation, P concentration of soil solution had increased by a factor of > 10 at the highest humic level (50 g humics kg^?1 soil), accompanied by a similar increase in Fe and Al concentrations. Soil samples with 0, 10, 30, 50 g humics kg^?1 soil were planted with red clover and ryegrass. Red clover showed a small increase of shoot yield and a moderate increase of P uptake after humics addition. High humics levels increased slightly Fe concentration in the shoots but strongly that of Mn leading to Mn toxicity. Ryegrass showed a strong increase in shoot yield after humics addition of about 150 % at the highest humics level compared to the control without humics. At each humic level, P application (100 mg kg^?1 soil) had no effect on P uptake of red clover and a small effect on P uptake by ryegrass. The relatively small effect of humics and P application on shoot yield of clover compared to grass can be explained by chemical P mobilization of red clover via exudation of citrate (about 12 μmol citrate g^?1 soil). This agrees with the finding that P solubility increased in the soil under red clover but not under ryegrass from the first to the second harvest, indicating that red clover mobilized P.     

Remediation of Atrazine-contaminated Soil and Water by Nano Zerovalent Iron

Atrazine-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of nano zerovalent iron (nano ZVI) to dechlorinate atrazine (2-chloro-4ethylamino-6-iso-propylamino-1,3,5-triazine) in contaminated water and soil. This study determined the effects of iron sources, solution pH, Pd catalyst and presence of Fe or Al sulfate salts on the destruction of atrazine in water and soil. Our results indicate nano ZVI can be successfully used to remediate atrazine in water and soil. Aqueous solution of atrazine (30 mg l^?1) was treated with 2% (w/v) of nano ZVI and 5% (w/v) of commercial ZVI. Although, iron dose in nano ZVI treatment was less than that in commercial ZVI treatment, atrazine destruction kinetic rate (k _obs) of nano ZVI treatment (1.39 days^?1) was around seven times higher than that of commercial ZVI treatment (0.18 days^?1). Reductive dechlorination was the major process in destruction of atrazine by nano ZVI. The dechlorination product was 2-ethyl-amino-4-isopropylamino-1,3,5-triazine. Lowering the pH from 9 to 4 increased the destruction kinetic rates of atrazine by nano ZVI. Moreover, nano ZVI/Pd enhanced destruction kinetic rates of atrazine (3.36 day^?1). Pd played the important role as a catalyst during treatment of atrazine by nano ZVI. Atrazine destruction kinetic rates were greatly enhanced in both contaminated water and soil treatments by nano ZVI when sulfate salts of Fe(II), Fe(III) or Al(III) was add with the following order of removal rates: Al (III) (2.23 day^?1) > Fe (III) (2.04 day^?1) > Fe(II) (1.79 day^?1). The same results were found in atrazine-nano ZVI-soil incubation experiments.     

Der Einfluß der natürlichen organischen Substanzen auf die Metallverteilung zwischen Boden und Bodenlösung in einem sauren Waldboden

The influence of organic matter in the translocation of metals between soil and soil solution of an acid forest soil Water extracts were prepared from soil samples which were collected from a soil profile showing very little variation in the texture down to a depth of 120 cm and thus only little translocation of clay in the soil profile. The aim of the study was to describe the distribution between soil and soil solution of several metals like Cu, Pb, Cd, Zn, Al and Mn as a function of humic substances, electrolyte concentration and pH. From the experimental results the following hypothesis on the reaction mechanisms involving metals and humus derived substances has been deduced. The metals Cu, Fe, Al and Pb are mobilized through complexation by soluble humus substances in addition to the usual pH dependent desorption and dissolution of hydroxides. This mobilization determines the solution concentration of Cu and Fe at pH > 3.7 and Al and Pb at pH > 4.2. Al, Fe and Pb are complexed selectively by high molecular weight humus derived substances which undergo adsorption on soil mineral surfaces. Cu interacts with low molecular weight humus derived substances which are not easily adsorbed by the mineral surfaces. Zn, Cd and Mn primarily undergo sorption and are thus controlled by pH and electrolyte concentration of solutions because their complexation with humus derived substances seems to be weak or nonexistant. It is further postulated that the humus derived substances mobilize Al³⁺ and Fe³⁺ ions. By this, other metals like Cd, Zn, Mn, Ca and Mg can occupy the free exchange sites.     

Kinetic Speciation of Ni(II) in Model Solutions and Freshwaters: Competition of Al(III) and Fe(III)

The competing ligand exchange method was used to investigate the competitive binding of Ni(II) by Al(III) and Fe(III) in model aqueous solutions and freshwaters. Graphite furnace atomic absorption spectrometry and adsorptive cathodic stripping voltammetry were used to monitor the rate of uptake of the Ni by Chelex 100 chelating resin and dimethylglyoxime as the competing ligands, respectively. The results have revealed that Ni(II)–humate complexes were more labile in presence of the mixture of Al(III) and Fe(III), compared to the lability of the Ni(II)–humate complexes when only one of the two, Al(III) or Fe(III), was present. The environmental significance of this work is that in model solutions simulating freshwater containing humic substances and the target trace metal Ni(II) and cations, Al(III) and Fe(III), the competitive binding of Ni(II), Al(III) and Fe(III) by humic substances makes Ni(II)–humate complexes labile, releasing free Ni²⁺–aqua complex, which reported to be toxic.     

Phosphate aquisition by red clover and black mustard on a humic podzol

Recent investigations have shown that phosphate (P) mobilization by root exudates is an important feature of genotypes to acquire P even in soils of low‐P availability. We, therefore, investigated P mobilization processes in the rhizosphere of red clover (Trifolium pratense L.) and black mustard (Brassica nigra L.) on a humic podzol. As measured by the Kuchenbuch‐Jungk method (Kuchenbuch and Jungk, 1982), both species accumulated similar quantities of citrate (12 μmol/g soil) in the rhizosphere in about 1 mm distance from the soil‐root interface. Despite of similar concentrations of P‐mobilizing citrate in the rhizosphere of both species, red clover took up nearly the two‐fold of P compared to black mustard. Differences in rhizosphere pH were determined between both species. Black mustard did not acidify the rhizosphere, whereas red clover decreased the pH in the rhizosphere from 5.8 to about 4.0 (in 0.01M CaCl₂). The simultaneous acidification and excretion of citrate compared to citrate excretion alone had consequences for P mobilization processes in the rhizosphere. Phosphate mobilization from the soil solid phase was higher at higher pH. Thus, the citrate‐induced P desorption was not the limiting step in P acquisition by red clover and black mustard. Calculations of P distribution in the soil solution between free ortho‐P and humic‐associated P showed that at higher pH most of the P was associated with dissolved humic substances, whereas at pH < 5, most of the P was present as free ortho‐P. These P species can readily be taken up by the roots whereas humic‐associated P must probably be desorbed from the humic surface before uptake. Phosphate species calculations, therefore, explained the higher P uptake of red clover compared to black mustard. Aluminum species distribution calculations in the soil solution further show that even at pH < 5.0 in the soil solution, citrate strongly complex Al and thereby reduce the activity of monomeric Al species. The excretion of citrate can, therefore, counteract the root induced acidification of the rhizosphere with respect to Al toxicity.     

Separation of phosphorus bound to organic matrices from inorganic phosphorus in alkaline soil extracts by ultrafiltration

Abstract

A method is described to separate inorganic phosphorus from phosphorus bound to humic substances in alkaline soil extracts. The method consists of the addition of polyethylenimine as a flocculant to the soil extract and subsequent ultrafiltration through 2September 1991 D cellulose acetate membranes. Inorganic P (P_i) is determined in the ultrafiltrate, organic P (P_o) as the difference of total P, measured prior to ultrafiltration, and P_i.

The procedure removed more than 90% of the organic carbon extracted at pH 11.2 from humic sandy soils. Substantial amounts of P_i determined in this way were released as P_i from the organic matrix when the alkaline extracts were acidified to pH < 4.0. The usual photometric methods for determining P_i require acidification of the solution to pH < 1.0. Therefore, if alkaline soil extracts are analysed without ultrafiltration, P_o may be seriously underestimated.

Acidification of the alkaline soil extracts to pH < 4.0 resulted also in a release of high percentages of Al and Fe bound to organic matter, the relation to pH being similar to that found for P_i. It is therefore concluded that the main part of P_o is bound to the organic matrix by Al or Fe bridges.     

A Study on Al(III) and Fe(II) Ions Sorption by Cattle Manure Vermicompost

Cattle manure vermicompost has been used for the adsorption of Al(III) and Fe(II) from both synthetic solution and kaolin industry wastewater. The optimum conditions for Al(III) and Fe(II) adsorption at pH?2 (natural pH of the wastewater) were particle size of ≤250?µm, 1 g/10 mL adsorbent dose, contact time of 4 h, and temperature of 25°C. Langmuir and Freundlich adsorption isotherms fitted reasonably well in the experimental data, and their constants were evaluated, with R ² values from 0.90 to 0.98. In synthetic solution, the maximum adsorption capacity of the vermicompost for Al(III) was 8.35 mg g^?1 and for Fe(II) was 16.98 mg g^?1 at 25°C when the vermicompost dose was 1 g 10 mL^?1, and the initial adjusted pH was 2. The batch adsorption studies of Al(III) and Fe(II) on vermicompost using kaolin wastewater have shown that the maximum adsorption capacities were 1.10 and 4.30 mg g^?1, respectively, at pH?2. The thermodynamic parameter, the Gibbs free energy, was calculated for each system, and the negative values obtained confirm that the adsorption processes were spontaneous.     

Forms of soluble aluminium in acidic topsoils estimated by ion chromatography and 8-hydroxyquinoline and their correlation with growth of subterranean clover

Labile Al in the soil solution measured by 8-hydroxyquinoline (Al_HQ) was a better predictor of plant growth than trivalent Al (Al_IC³⁺) measured by ion chromatography (IC). HQ reacted with some organic Al complexes which did not separate during chromatography. In the presence of oxalic acid, Al_HQ was greater than Al_IC³⁺, which was the same as the greater than Al³⁺ (Al³⁺_Calc), whereas in the presence of citric acid, Al_HQ was greater than Al_IC³⁺, and both were greater than Al⁺³_Calc, In extracts of soils that had been acidified, Al³⁺_IC was less than Al_HQ, which was similar to Al³⁺_Calc, when it was assumed that the only complexing ligands were OH^? and F^?. The proportion of Al³⁺_IC in the soil solutions decreased more than Al_HQ as the pH increased. Organic ligands appeared to form complexes with Al at the expense of AIF complexes. Forms of Al detected by IC differed in CaCl₂ extracts and soil solutions. Al_HQ in the CaCl₂ extracts and soil solution were closely correlated, although the proportion of Al_HQ was higher in the CaCl₂ extracts. And soil solutions. Al_HQ in the CaCl₂ extracts and soil solution were closely correlated, although the proportion of Al_HQ was higher in the CaCl₂ extracts.     

Organic Amendment Effects on the Transformation and Fractionation of Aluminum in Acidic Sandy Soil

Addition of organic amendments can alleviate the level of aluminum (Al) phytotoxicity in acid soils by affecting the nature and quantity of Al species. This study evaluated the transformation of Al in an acidic sandy Alaquod soil amended with composts (10 and 50 g kg^?1 soil of yard waste, yard + municipal waste, GreenEdge^®, and synthetic humic acid) based on soil Al fractionation by single and sequential extractions. Though the organic compost amendments increased total Al in soil, they alleviated Al potential toxicity in acidic soil by increasing soil pH and converting exchangeable Al to organically bound and other noncrystalline fractions, stressing the benefits of amending composts to improve acid soil fertility. The single‐extraction method appears to be more reliable for exchangeable Al than sequential extraction because of the use of nonbuffered pH extract solution.     

The effects of low pH,low calcium concentrations and elevated aluminium concentrations on sodium fluxes in brown trout,Salmo Trutta L.

The effects of pH (c. 7.0, 5.4, 4.5 and 4.0), nominal Al levels (0 and 8 μmol L^?1) and Ca levels (10 and 50 μmol L^?1) on Na influx, efflux and netflux of brown trout have been investigated using artificial lake water of known composition. Low pH had little effect on influx, but tended to increase efflux, particularly in the low Ca treatments. A nominal addition of 8 μmol Al L^?1 at pH 4.5 and 4.0 reduced influx significantly. Efflux was unaffected. Aluminium addition at pH c. 7.0 and 5.4 had no such effect. The measured Al concentrations at the end of the static 8 hr flux measuring experiments were markedly lower than the nominal amount of A1 added to the start.     

Factors affecting the soil sorption of iodine

Iodine-129 is an important radionuclide released from nuclear facilities because of its long radioactive half-life and its environmental mobility. Its retention in surface soils has been linked to pH, organic matter, and Fe and Al oxides. Its inorganic solution chemistry indicates I will most likely exist as an anion. Three investigations were carried out to provide information on the role of the inorganic and organic chemistry during sorption of I by soil. Anion competition using Cl^? showed that anion exchange plays a role in I sorption in both mineral and organic soils. The presence of Cl decreased the loss of I^? from solution by 30 and 50% for an organic and a carbonated sandy soil respectively. The I remaining in solution was associated primarily with dissolved organic carbon (DOC). The loss rate from solution appears to depend on two reactions of I with the soil solids (both mineral and organic) creating both a release to and a loss from solution, and the reaction of I with the DOC (from very low to high molecular weight). Composition analyses of the pore water and the geochemical modelling indicate that I sorption affects the double-charged anion species in solution the most, particularly SO₄ ^?. Iodide introduced to natural bog groundwater at three concentrations (10^?3, 10^?1 and 10 meq L^?1) remained as I^? and was not lost from solution quickly, indicating that the association of I with DOC is slow and does not depend on the DOC or I concentration. If sorption of I to soil solids or DOC is not sensitive to concentration, then stable I studies, which by necessity must be carried out at high environmental concentrations, can be linearly extrapolated to radioactive I at much lower molar concentrations.     

Sodium hypochlorite oxidation reduces soil organic matter concentrations without affecting inorganic soil constituents

Oxidative treatment can isolate a stable organic matter pool in soils for process studies of organic matter stabilization. Wet oxidation methods using hydrogen peroxide are widely used for that purpose, but are said to modify poorly crystalline soil constituents. We investigated the effect of a modified NaOCl oxidation (pH 8) on the mineral composition of 12 subsoils (4.9–38.2 g organic C kg^?1) containing varying amounts of poorly crystalline mineral phases, i.e. 1.1–20.5 g oxalate‐extractable Fe kg^?1, and of different phyllosilicate mineralogy. Post‐oxidative changes in mineral composition were estimated by (i) the determination of elements released into the NaOCl solution, (ii) the difference in dithionite‐ and oxalate‐extractable Si, Al and Fe, and (iii) the specific surface areas (SSAs) of the soils. The NaOCl procedure reduced the organic C concentrations by 12–72%. The amounts of elements released into the NaOCl extracts were small (≤ 0.14 g kg^?1 for Si, ≤ 0.13 g kg^?1 for Al, and ≤ 0.03 g kg^?1 for Fe). The SSA data and the amounts of dithionite‐ and oxalate‐extractable elements suggest that the NaOCl oxidation at pH 8 does not attack pedogenic oxides and hydroxides and only slightly dissolves Al from the poorly crystalline minerals. Therefore, we recommend NaOCl oxidation at pH 8 for the purpose of isolating a stable organic matter pool in soils for process studies of organic matter stabilization.     

Orthophosphate and organic phosphate in the soil solution of four sandy soils in relation to pH‐evidence for humic‐FE‐(AL‐) phosphate complexes

Abstract

Soil from the Ap‐horizon of four acid sandy soils differing mainly in Corg content was adjusted to pH values between 3 and 7.5 with NaOH and HCl respectively and incubated for two weeks. Afterwards, displaced soil solution was obtained and analyzed.

The concentrations of Fe, Al, and P showed a broad minimum in the pH range from 4 to 6. The concentration of these elements strongly increased with the increase of pH to 7.5. Acidification below pH values of 4 led to a slight increase.

Separation of dissolved organic carbon by ultrafiltration before the photometric orthophosphate determination decreased measured concentrations in comparison to direct determination in two of the four soils. This decrease was more pronounced for soil solutions with higher concentrations of organic carbon. The effect of acid hydrolysis of organic phosphorus during orthophosphate determination can be explained by existence of humic‐Fe‐(Al phosphate complexes in the soil solution. These complexes can account for more than 50% of the total organic P in solution.     

Using Low-Cost Iron Byproducts from Automotive Manufacturing to Remediate DDT

Water, soil and sediment contaminated with DDT poses a threat to the environment and human health. Previous studies have shown that zerovalent iron (ZVI) can effectively remediate water contaminated with pesticides like DDT, metolachlor, alachlor. Because the type of iron can significantly influence the efficiency and expense of ZVI technology, finding a cheaper and easily available iron source is one way of making this technology more affordable for field application. This study determined the effects of iron source, solution pH, and presence of Fe or Al salts on the destruction of DDT. Batch experiments demonstrated successful removal of DDT (>95% in 30 d) in aqueous solutions by three different iron sources with the following order of removal rates: untreated iron byproduct (1.524 d^?1) > commercial ZVI (0.277 d^?1) > surface-cleaned iron byproduct (0.157 d^?1). DDT removal rate was greatest with the untreated iron byproduct because of its high carbon content resulted in high DDT adsorption. DDT destruction rate by surface-cleaned iron byproduct increased as the pH decreased from 9 to 3. Lowering solution pH removes Fe (III) passivating layers from the ZVI and makes it free for reductive transformations. By treating DDT aqueous solutions with surface-cleaned iron byproduct, the destruction kinetics of DDT were enhanced when Fe(II), Fe(III) or Al(III) salts were added, with the following order of destruction kinetics: Al(III) sulfate > Fe(III) sulfate > Fe(II) sulfate. Cost analysis showed that the cost for one kg of surface-cleaned iron byproduct was $12.33, which is less expensive than the commercial ZVI. Therefore, using surface-cleaned iron byproduct may be a viable alternative for remediating DDT-contaminated environments.     

Factors Affecting the Formation,Nature, and Properties of Iron Precipitation Products at the Soil–Root Interface

Abstract

A number of iron oxides (hematite, goethite, lepidocrocite, maghemite, and magnetite) or short‐range ordered precipitates (ferrihydrite) may be found in soil environments, but in the rhizosphere the presence of organic ligands released by plants (exudates) or microorganisms promote the formation of ferrihydrite. Iron ions are liberated into soil solution by acidic weathering of minerals and then precipitated either locally or after translocation in soil environments. Humic and fulvic acids as well as organic substances produced by plants and microorganisms are involved in the weathering of primary minerals. Organic compounds play a very important role in the hydrolytic reactions of iron and on the formation, nature, surface properties, reactivity, and transformation of Fe oxides. Organic substances present in the rhizosphere interact with Fe promoting the formation of ferrihydrite and organo‐mineral complexes. The solubility of Fe precipitation products is usually low. However, the formation of soluble complexes of Fe(II) or Fe(III) with organic ligands, usually present in the rhizosphere increases the solubility of Fe‐oxides. Mobilization of Fe from Fe oxides by siderophores is of great importance in natural systems. They can form stable Fe(III) complexes (pK up to 32) and thus mobilize Fe from Fe(III) compounds. These higher Fe concentrations are important for the supply of Fe to plant roots which excrete organic acids at the soil–root interface. Iron oxides adsorb a wide variety of organic and inorganic anions and cations, which include natural organics, nutrients, and xenobiotics. There is competition between anions and cations for the surfaces of Fe‐oxides. Root exudates suppress phosphate or sulfate adsorption on Fe‐oxides. This is a mechanism by which plant roots mobilize adsorbed phosphate and improve their phosphate supply. Anions adsorption on iron oxides modify their dispersion/flocculation behavior and thus their mobility in the soil system. That can increase or decrease the possibility of contact between Fe‐oxides and organics or organisms able to dissolve them.