Solid Phase Extraction Method for Selective Determination of Phthalate Esters in the Aquatic Environment

The use of solid phase extraction and capillary GLC provides thebasis for the selective determination of phthalate ester plasticizers in rivers and marine water samples. Of the severalsolvent ratios (methanol in dichloromethane) used for selective elution of phthalate esters from the C18 solid phase glass catridge, the 50/50 ratio, CH₃OH in CH₂Cl₂ (v/v)gave the best result. The method was tested on river and marinewater samples that receive effluent from industries that use phthalate esters. The rivers and marine water samples were grossly polluted as several phthalate esters, for example, dimethyl (DMP), diethyl (DEP), dibutyl (DBP) and diethylhexyl (DEHP)were present at 0.03–2306±9.4 μg L^-1. A study on uncontaminated water was done to establish background levels.     

Biodegradability of Di(2-Ethylhexyl) Phthalate by Pseudomonas Fluorescens FS1

Di(2-ethylhexyl)phthalate (DEHP), one of high-molecular weightphthalate esters (PAEs), is used in the manufacturing of polyvinylchloride (PVC) resins, polyvinyl acetate, cellulosics,and polyurethanes, and contributes to environmental pollution. In this article, the characteristics of DEHP biodegradation by aneffective degradation bacterium, Pseudomonasfluorescens FS1 that isolated from the activated sludge at a petrochemicalfactory, was capable of using phthalate esters as the sole carbonand energy source, were investigated. Experimental results showedthat the biodegradation of DEHP by P. fluorescens FS1 could be described by the first-order reaction model, whichcould be expressed as: lnC = –0.0688t + A, and the half-life ofDEHP biodegradation was 10.07 d when the initial concentrations of DEHP were less than 50 mg L^-1. The inhibition effects ofDEHP as a substrate had become predominant above the concentration of 50 mg L^-1. The PAEs-degrading enzyme of P. fluorescens FS1, mainly located in the soluble part andthe particle of cytoplasm, was an intracellular enzyme. The metabolites of DEHP degradation by P. fluorescens FS1, which monoester, phthalic acid, benzonic acid, phenol, wereextracted using dichloromethane at different time intervals and identified by the GC-MS. The tentative pathway proposed for degradation of DEHP by P. fluorescens FS1 under aerobic condition is monoester in the beginning, further enzymatic degradation of the monoester produces phthalic acid, benzonic acid, phenol and finally CO₂ and H₂O.     

Sorption of 2,4-D and other phenoxy herbicides to soil, organic matter, and minerals

Purpose

We review 2,4-dichlorophenoxyacetic acid (2,4-D) and other phenoxy herbicide sorption experiments.

Methods

A database with 469 soil–water distribution coefficients K _d (in liters per kilogram) was compiled: 271 coefficients are for the phenoxy herbicide 2,4-D, 9 for 4-(2,4-dichlorophenoxy)butyric acid, 18 for 2-(2,4-dichlorophenoxy)propanoic acid, 109 for 2-methyl-4-chlorophenoxyacetic acid, 5 for 4-(4-chloro-2-methylphenoxy)butanoic acid, and 57 for 2-(4-chloro-2-methylphenoxy)propanoic acid. The following parameters characterizing the soils, solutions, or experimental procedures used in the studies were also compiled if available: solution CaCl₂ concentration, pH, pre-equilibration time, temperature, soil organic carbon content (f _oc), percent sand, silt and clay, oxalate extractable aluminum, oxalate extractable iron (Oxalate Fe), dithionite–citrate–bicarbonate extractable aluminum, dithionite–citrate–bicarbonate extractable iron (DCB Fe), point of zero negative charge, anion exchange capacity, cation exchange capacity, soil type, soil horizon or depth of sampling, and geographic location. K _d data were also compiled characterizing phenoxy herbicide sorption to the following well-defined sorbent materials: quartz, calcite, α-alumina, kaolinite, ferrihydrite, goethite, lepidocrocite, soil humic acid, Fluka humic acid, and Pahokee peat.

Results

The data review suggests that sorption of 2,4-D can be rationalized based on the soil parameters pH, f _oc, Oxalate Fe, and DCB Fe in combination with sorption coefficients measured independently for humic acids and ferrihydrite, and goethite.

Conclusions

Soil organic matter and iron oxides appear to be the most relevant sorbents for phenoxy herbicides. Unfortunately, few authors report Oxalate Fe and DCB Fe data.     

Enhanced dissipation of DEHP in soil and simultaneously reduced bioaccumulation of DEHP in vegetable using bioaugmentation with exogenous bacteria

The widely used plastic film containing di(2-ethylhexyl) phthalate (DEHP) in agriculture has caused serious soil pollution and poses risks to human health through the food chain. An effective DEHP degradation bacteria, Microbacterium sp. J-1, was newly isolated from landfill soil. Response surface methodology was successfully employed for optimization resulting in 96% degradation of DEHP (200 mg L^?1) within 5 days. This strain degraded DEHP by hydrolysis of the ester bond and hydroxylation of the aromatic ring to form 2-ethyl hexanol, mono-(2-ethylhexyl) phthalate, phthalate acid, and protocatechuic acid, and subsequently transformed these compounds with a maximum specific degradation rate (q _max), half-saturation constant (K _s ), and inhibition constant (K _i ) of 1.46 day^?1, 180.2 mg L^?1, and 332.8 mg L^?1, respectively. Bioaugmentation of DEHP-contaminated soils with the strain J-1 greatly enhanced the DEHP dissipation rate (~88%). Moreover, this strain could efficiently colonize the rhizosphere soil of inoculated vegetables and further enhanced DEHP degradation (~97%), leading to a significant decrease (>70%) in DEHP accumulation in shoots and roots of the inoculated vegetables compared to uninoculated vegetables. The results highlighted the roles of the inoculated exogenous bacteria in simultaneously bioremediating contaminated soils and reducing bioaccumulation of DEHP in the edible part of the vegetable for food safety.     

Adsorption of Dimethyl Phthalate on Marine Sediments

Experiments were performed to investigate the sorption behaviors of dimethyl phthalate on marine sediments. The sorption of dimethyl phthalate on marine sediments reached equilibrium within 10 h. The sorption behavior of dimethyl phthalate on HCl-treated and untreated sediments accorded well with the linear sorption isotherm. The sorption occurred primarily via partition function of organic carbon of marine sediments. The sorption behavior of dimethyl phthalate on H₂O₂-treated sediment was nonlinear and conformed to Freundlich isotherm. Sorption of dimethyl phthalate on H₂O₂-treated sediment was chiefly through surface function of clay in marine sediments. Salinity of seawater had an important effect on the sorption of dimethyl phthalate. As the salinity of seawater increased, both the partitioning coefficients K _d and empirical constant K would increase.     

胡敏酸对铵钾在粘土矿物上交互作用的影响

Interaction of ammonium (NH+4) and potassium (K+) is typical in field soils. However, the effects of organic matter on interaction of NH+4 and K+have not been thoroughly investigated. In this study, we examined the changes in major physicochemical properties of three clay minerals (kaolinite, illite, and montmorillonite) after humic acid (HA) coating and evaluated the influences of these changes on the interaction of NH+4 and K+on clay minerals using batch experiments. After HA coating, the cation exchange capacity (CEC) and specific surface area (SSA) of montmorillonite decreased significantly, while little decrease in CEC and SSA occurred in illite and only a slight increase in CEC was found in kaolinite. Humic acid coating significantly increased cation adsorption and preference for NH+4, and this effect was more obvious on clay minerals with a lower CEC. Results of Fourier transform infrared spectrometry analysis showed that HA coating promoted the formation of H-bonds between the adsorbed NH+4 and the organo-mineral complexes. HA coating increased cation fixation capacity on montmorillonite and kaolinite, but the opposite occurred on illite. In addition, HA coating increased the competitiveness of NH+4 on fixation sites. These results showed that HA coating affected both the nature of clay mineral surfaces and the reactions of NH+4 and K+with clay minerals, which might influence the availability of nutrient cations to plants in field soils amended with organic matter.     

Caesium sorption—desorption in clay—humic acid systems

Soaking for 7 d with 0.05 M NaCl resulted in less caesium being sorbed by bentonite and kaolinite, but more by illite, compared to soaking for 2 d prior to addition of Cs. Overall the amount of Cs sorbed by the three clays was in the order bentonite > illite > kaolinite. Addition of humic acid to the clays depressed the sorption of Cs by all three clays, with illite showing the greatest effect. Desorption of added Cs was not totally reversible. The presence of humic acid resulted in an enhanced desorption of Cs from bentonite and to a lesser extent kaolinite. This enhanced desorption in the presence of humic acid was not seen for illite. The order of Cs retention following desorption for both clay and clay/ humic-acid mixtures was illite > bentonite > kaolinite. A single K_d value could not describe the whole isotherm, but individual values were calculated at different Cs concentrations to cover the range of the isotherm. K_d values for desorption were higher than the corresponding K_d for sorption. For both sorption and desorption, the presence of humic acid resulted in lower K_d values than in its absence.     

Influence of natural and synthetic humic substances on the activity of urease

The activity of a purified urease, obtained from Bacillus pasteurii, was inhibited by humic and fulvic acids obtained from an agricultural soil. Enzyme kinetic studies showed that the humic substances affected the affinity of the enzyme for its substrate (K_m) and the maximum velocity of the reaction (V_max). The V_max was inhibited to the same extent by both humic (HA) and fulvic (FA) acids, the precise effect depending on the pH and concentration of humic substance. At pH 4.0, HA concentrations of 25 pg cm^?3 and 10 μg cm^?3 inhibited the V_max by 38.5% and 20% respectively. HA and FA had similar effects on the K_m but in this case the lowering of the affinity of the enzyme for its substrate was not concentration dependent in the range 0–25 μg cm^?3 of humic substance. Typically, the affinity was decreased from a K_M of 50 mM in the control to 67 mM in the presence of HA and FA. The effects were not due primarily to the ash or N contents of the humic substances because de-ashed humic acid and synthetic model humic (made from catechol, guaiacol, pyrogallol, resorcinol and protocatechuic acid) and fulvic acid (made from polymaleic acid), containing virtually no ash or N, were equally as effective. The effect was not related to the phenolic monomers which, before polymerization, had no effect on urease activity.     

电荷辅助氢键对腐殖酸分子量和溶解性的影响

采用体积排阻色谱和总有机碳分析法,分别测定腐殖酸体系中加入盐酸、甲酸、乙酸和丙酸后其分子量和溶解性发生的变化;通过分析抗坏血酸、苯甲酸、苯酚和邻苯二酚4种模型化合物在甲酸影响下的紫外光谱,以验证电荷辅助氢键的存在。结果表明:小分子有机酸能够明显降低腐殖酸的分子量;此外,当腐殖酸体系pH接近小分子有机酸的pKa时(DpKa<0.5),腐殖酸溶解性明显增大。小分子有机酸可能与腐殖酸之间形成电荷辅助氢键,从而打破弱作用力维持的腐殖酸超分子的稳态结构,导致腐殖酸分子量的降低和溶解性的增加;且弱酸与有机物之间的pKa相差越小,形成的电荷辅助氢键能量越高,腐殖酸分子结构受到的扰动程度越大。一维紫外光谱和同步二维相关紫外光谱分析进一步表明,小分子有机酸可能与pKa接近的化合物之间形成电荷辅助氢键,整体跃迁所需能量提高,造成低波长吸收增大而高波长吸收减小的结果。     

Effect of humic acid on copper adsorption by Kaolin

Varying amounts of humic acid (Na-salt; 0 to 10 ppm) were first equilibrated with a dilute suspension of H⁺ -Kaolin and then with spiked (high activity radioactive ⁶⁴Cu) water. After filtration, through a 0.45 µm Millipore membrane, the amount of radioactivity on the filter and the filtrate was measured separately using a Gamma ray well counter. Adsorption of Cu (expressed as distribution coefficient — K _d ) was plotted against humic acid concentration. K _d values decreased sharply upto 1 ppm humic acid concentration and thereafter remained constant up to 10 ppm.     

Complexation of Cu2+ and Pb2+ by peat and humic acid

The binding of metal to humic substances is problematical. The approaches for studying metal binding to organic matter are briefly reviewed. Ion-selective electrodes (Cu²⁺ and Pb²⁺) were used to measure metal complexation by a whole peat and an extracted humic acid (HA) fraction. Scatchard plots and calculation of incremental formation constants were used to obtain values for the binding constants for the metals onto both peat and HA. Both the peat and the humic acid had a larger maximum binding capacity for Pb²⁺ than for Cu²⁺ (e.g. at pH = 5 HA gave 0·188 mmol Cu²⁺ g^?1 and 0·564 mmol Pb²⁺ g^?1: peat gave 0·111 mmol Cu²⁺ g^?1 and 0·391 mmol Pb²⁺ g^?1). Overall, the humic acid had a larger metal binding capacity, suggesting that extraction caused conformational or chemical changes. The binding constants (K₁) for Cu²⁺ increased with increasing pH in both peat and humic acid, and were larger in the peat at any given pH (e.g. at pH = 5 HA gave log K₁= 2·63, and peat gave log K¹= 4·47 for Cu²⁺). The values for Pb²⁺ showed little change with pH or between peat and humic acid (e.g. at pH = 5 HA gave log K¹= 3·03 and peat gave log K¹= 3·00 for Pb²⁺). In the peat, Cu²⁺ may be more able to bind in a 2:1 stoichiometric arrangement, resulting in greater stability but smaller binding capacity, whereas Pb²⁺ binds predominantly in a 1:1 arrangement, with more metal being bound less strongly. Whole peat is considered to be more appropriate than an extracted humic acid fraction for the study of heavy metal binding in organic soils, as this is the material with which metals introduced into an organic soil would interact under natural conditions.     

The Oxidation of Di-(2-Ethylhexyl) Phthalate (DEHP) in Aqueous Solution by UV/H2O2 Photolysis

The oxidation of di-(2-ethylhexyl) phthalate (DEHP) in solution using UV/H₂O₂ and direct UV photolysis are analyzed in this study. It was found that DEHP was 100% removal in the solution by 180-min UV/H₂O₂ treatment and 73.5% removal by 180-min direct UV photolysis. The effect of different factors, such as DEHP concentration, H₂O₂ concentration, and UV light intensity, on photochemical degradation was investigated. The degradation mechanism of DEHP and the acute toxicity of intermediates were also studied. The photochemical degradation process was found to follow pseudo-first-order kinetics. The results of our study suggested that the concentration with 40 mg/L H₂O₂ and 5 μg/mL DEHP in the solution at pH 7 with 10.0?×?10^?6 Einstein l^?1?s^?1 UV was the optimal condition for the photochemical degradation of DEHP. The photochemical degradation with UV/H₂O₂ can be an efficient method to remove DEHP in wastewater.     

Degradation of Di-(2-ethylhexyl) Phthalate (DEHP) by TiO2 Photocatalysis

The photocatalytic degradation of di-(2-ethylhexyl) phthalate (DEHP) in solution using titanium dioxide (TiO₂) was analyzed in this study. It was found that DEHP was completely removed in the solution after 150 min irradiation. The effect of different factors, such as photocatalyst amount, DEHP concentration, light intensity, pH, and temperature on photocatalytic degradation was investigated. The degradation mechanism of DEHP with proton and hydroxyl radicals oxidation were also studied. It is suggested that either ethylhexyl or ester chain scissions of the aliphatic part of DEHP was the dominant degradation mechanism of the process. The photocatalytic degradation process was well described by first-order reaction. The final mineralization product was carbon dioxide and the intermediate products were identified by GC-MS. Thus, the photocatalytic degradation treatment of DEHP in wastewater is a relative simple and fast method.     

The effects of three phthalate esters on the larval development of the grass shrimp Palaemonetes pugio (Holthuis)

The effects of three phthalic acid esters, dimethyl phthalate (DMP), di-n-butyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP) on survival and development rate of larvae of the grass shrimp Palaemonetes pugio were investigated. Only 100 ppm DMP and 10 to 50 ppm DBP were acutely toxic to the larvae. DMP at a concentration of 100 ppm significantly increased the duration of larval development to the first postlarval stage. DEHP concentrations up to 1 ppm (the solubility limit of this ester) were without effect on either survival or development rate of the larvae. Phthalate esters were not detectable at or above the 2 ppm level in the tissues of larvae chronically exposed to phthalates for the duration of larval development, suggesting active metabolism of phthalates by this species.     

Sorption of humic acid on Fe oxides,bacteria, and Fe oxide-bacteria composites

Purpose

Sorption of humic substances on other soil components plays an important role in controlling their function and fate in soil. Sorption of humic substances by individual soil components has been studied extensively. However, few studies reported the sorption characteristic of humic substances on composites of soil components. This study aimed to investigate the sorption characteristics of humic acid on Fe oxide-bacteria composites and improve the understanding on the interaction among humic substance Fe oxide bacteria in soil.

Materials and methods

Humic acid was purchased from Sigma-Aldrich and was purified. Hematite and ferrihydrite were synthesized in the lab. Bacillus subtilis and Pseudomonas putida were cultivated in Luria-Broth medium and harvested at stationary growth phase. Batch sorption experiments were carried out at pH 5.0. Various amounts of humic acid were mixed with 20 mg of Fe oxide, bacteria, or Fe oxide-bacteria composite (oxide to bacteria of 1:1) in 10 mL of KCl (0.02 mol L^?1) to construct sorption isotherms. The effects of phosphate concentration and addition order among humic acid, Fe oxide, bacteria on the sorption of humic acid were also studied. The sorption of humic acid was calculated by the difference between the amount of humic acid added initially and that remained in the supernatant.

Results and discussion

The maximum sorption of humic acid on hematite, ferrihydrite, B. subtilis and P. putida was 73.2, 153.5, 69.1, and 56.7 mg C g^?1, respectively. The maximum sorption of humic acid on examined Fe oxide-bacteria composite was 28.2–57.2 % less than the predicted values, implying that the sorption of humic acid was reduced by the interaction between Fe oxides and bacteria. The presence of phosphate exerted negligible influence on the sorption of humic acid on bacteria while it inhibited the sorption of humic acid on Fe oxides. On Fe oxide-bacteria composites, inhibiting influences followed by promoting or weak inhibiting effects of phosphate with increasing concentration on the sorption of humic acid were found.

Conclusions

The interaction between Fe oxides and bacteria reduced the sorption of humic acid; moreover, the reduction was greater by the interaction of bacteria with ferrihydrite than that with hematite. Phosphate exerted negligible and inhibiting influence on the sorption of humic acid by bacteria and Fe oxides, respectively. On Fe oxide-bacteria composites, humic acid sorption was initially inhibited and then promoted or weakly inhibited by phosphate with increasing concentration.     

胡敏酸对土壤和矿物粘粒分散的影响

研究了土壤胡敏酸(Humic acid)对红壤和黄棕壤以及高岭矿和蒙脱矿粘粒分散的影响。研究结果表明：土壤HA对Na⁺饱和的土壤及矿物粘粒分散作用很大。用H₂O₂除去土壤有机质后,粘粒分散明显下降。然而,添加少量HA后,又能显著地提高粘粒的分散性。这种现象在两种土壤中,红壤表现更为突出。Na⁺饱和的高岭矿粘粒分散性很差,而蒙脱矿粘粒分散性很强,这与它们所带电荷量有关。但是,添加少量HA后,高岭矿粘粒分散性急剧提高,而蒙脱矿的变化却很小。试验结果进一步表明：有机质HA对土壤和矿物粘粒分散作用受矿物类型的影响。     

Humic acid and biochar as specific sorbents of pesticides

Purpose

The aim of the research was to compare the effect of two types of organic sorbents—humic acid (HA) and biochar (BC)—in sorption-desorption processes of different polar pesticides, which residues are commonly present in arable soils and are potentially harmful for the environment. It also aims to advance the understanding of behavior of both ionizable and nonionizable pesticides in the presence of BC and HA in soils.

Materials and methods

Three different classes of pesticides were investigated: carbamates (carbaryl and carbofuran), phenoxyacetic acids (2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-methylphenoxyacetic acid (MCPA)), and aniline derivatives (metolachlor). Investigated humic acid was extracted by Shnitzer’s method from topsoil horizon of arable Gleyic Phaeozem. Biochar was produced from wheat straw in gasification process at 550 °C, remaining 30 s in the reactor. To obtain the experimental goal structural properties of both sorbents were determined and sorption-desorption experiments conducted. To the investigated organic matter samples (HA or BC), 10 or 15 mg L^?1 pesticide solutions in 10 mM CaCl₂ were added and the mixtures were shaken for 24 h. Afterwards, the samples were centrifuged and supernatants analyzed by LC-MS/MS for the pesticide content. Analogous experiment was performed for desorption studies (samples refilled with 10 mM CaCl₂).

Results and discussion

Humic acids exhibited strong affinity for the ionic substances, for which high-percentage uptake (74.6 and 67.9% initial dose of 2,4-D and MCPA, respectively) was obtained. Retention of nonionic carbamates on HA was much weaker (35.4% of carbofuran and 10.2% of carbaryl sorbed). Sorption of carbamates to BC was significantly reduced (76.4–84.3%) by the alkaline hydrolysis. Metolachlor was bound comparably strong both by HA (72.9%) and BC (70.2%), although different mechanisms governed its sorption. Noticeable desorption occurred only in the case of 2,4-D bound to HA (over 50%), whereas other studied compounds were released from HA within the range of 4.4–10.8% of the dose sorbed. Oppositely to HA, desorption of all studied pesticides from BC was completely inhibited, except for 2,4-D (3.7% desorbed).

Conclusions

Investigated humic acid has high affinity to polar, ionic pesticides of high water solubility, which are sorbed via specific interactions with HA functional groups. Studied biochar, due to its moderately hydrophobic character, preferentially attracts nonionic pesticides of relatively high logP values and low water solubility. Hydrophobic bonding is postulated as a main mechanism of their attraction to BC. Besides sorbent structural properties, pH is the main factor governing sorption equilibria in the studied mixtures.

     

Distribution Coefficient and Adsorption–desorption Rates of di (2-ethylhexyl) Phthalate (DEHP) onto and from the Surface of Suspended Particles in Fresh Water

The commonly used plastic softener, di (2-ethylhexyl) phthalate (DEHP), also a known Endocrine Disrupting Compound, was found contaminated in various aquatic environments, including river water in Thailand. The data of adsorption kinetics from this study indicated that DEHP can adsorb onto pure bentonite and natural suspended sediment with average adsorption rate constants of 0.0056 and 0.0039 min^?1 respectively. The average distribution coefficients between suspended particles and water found in this study for pure bentonite and natural suspended sediment were 0.045 and 0.043 l g^?1 respectively. Although the studies were carried out in pH 4.0, 7.0 and 10.0, there were no obvious influences of pH on adsorption rates and distribution coefficients of DEHP onto both pure bentonite and natural suspended particles. The desorption rate was very small and was estimated to be less than 0.03 μg min^?1. The results indicated that suspended sediment could become a long term release of DEHP and facilitate the transport of DEHP mainly due to fast adsorption rate and relatively high adsorption capacity.     

Iron oxide‐humic acid coprecipitates as iron source for cucumber plants

In soil, iron (Fe) solubility depends on complex interactions between Fe minerals and organic matter, but very little is known about plant availability of Fe present in Fe oxides associated with humic substances. For this purpose, this study investigates the effect of Fe mineral crystallinity in the presence of humic acids (HA) on Fe availability to plants. Four Fe–HA mineral coprecipitates were prepared, either in the presence or absence of oxygen, i.e., two goethite (G)‐HA samples containing large amounts of Fe as nanocrystalline goethite and ferrihydrite mixed phases, and two magnetite (M)‐HA samples containing crystalline magnetite. Bioavailability studies were conducted in hydroponic systems on cucumber plants (Cucumis sativus L.) grown under Fe deficient conditions and supplied with the Fe–HA coprecipitates containing goethite or magnetite. Results showed that plants grown in the presence of Fe–HA coprecipitates exhibited a complete recovery from Fe deficiency, albeit less efficiently than plants resupplied with Fe‐chelate fertilizer used as control (Fe‐diethylene triamine penta acetic acid, Fe‐DTPA). However, the supply with either G‐ or M–HA coprecipitates produced different effects on plants: G–HA‐treated plants showed a higher Fe content in leaves, while M–HA‐treated plants displayed a higher leaf biomass and SPAD (Soil–Plant Analysis Development) index recovery, as compared to Fe‐DTPA. The distribution of macronutrients in the leaves, as imaged by micro X‐ray fluorescence (µXRF) spectroscopy, was different in G–HA and M–HA‐treated plants. In particular, plants supplied with the poorly crystalline G–HA coprecipitate with a lower Fe/HA ratio showed features more similar to those of fully recovered plants (supplied with Fe‐DTPA). These results highlight the importance of mineral crystallinity of Fe–HA coprecipitates on Fe bioavailability and Fe uptake in hydroponic experiments. In addition, the present data demonstrate that cucumber plants can efficiently mobilize Fe, even from goethite and ferrihydrite mixed phases and magnetite, which are usually considered unavailable for plant nutrition.     

Crystallization of single and binary iron‐ and aluminum hydroxides affect phosphorus desorption

In acidic soils, phosphorus availability is affected by its strong affinity for mineral surfaces, especially Fe‐ and Al‐hydroxides. Plant roots have developed adaptive strategies to enhance the availability of phosphorus, including producing and exuding low molecular weight organic acids with a high affinity for phosphorus that competes with high molecular weight organic ligands formed during humification and mineralization. The aim of this study was to characterize the kinetics and mechanism of phosphorus desorption from Fe‐ and Al‐hydroxides of variable crystallinity, as well as binary Fe:Al‐hydroxide mixtures. Long‐term desorption experiments (56 days) were conducted with CaCl₂, CaSO₄, citric acid, and humic acid as competitive sorptives. CaCl₂ and CaSO₄ were selected as general inorganic sorptives and citric and humic acids were selected as organic ligands produced by organisms in the rhizosphere or following humification. The cumulative phosphorus desorption increased following the order CaCl₂ < CaSO₄ < humic acid < citric acid. Amorphous ferrihydrite and Fe‐rich Fe:Al‐hydroxides exhibited much less desorption when exposed to inorganic solutions than the crystalline and Al‐rich Fe:Al‐hydroxide mixtures. Models of the desorption data suggest phosphorus desorption with citric acid is diffusion‐controlled for ferrihydrite and Fe‐rich amorphous Fe:Al‐hydroxides. When humic acid was the sorptive, metal‐organic complexes accumulated in the solution. The results suggest organic compounds, especially citric acid, are more important for liberating phosphorus from Fe‐ and Al‐minerals than inorganic ions present in the soil solution.