Influence of Increasing Soil Copper Concentration on the Susceptibility of Phosphomonoesterase and Urease to Heat Disturbance

The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO₄ ^2– and PO₄ ^3–, surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by K _f was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota.     

Influence of organic matter on selenite sorption by Andosols

Abstract

The influence of soil organic matter on selenite sorption was investigated in the selenite adsorption capacity and the surface particle charge change by ligand exchange reaction using the hydrogen peroxide (H₂O₂) treatment and the ignition treatment of two Andosols. The removal of organic carbon (C) in soils accelerated selenite sorption, implying that organic matter of soils had negative influence on the selenite adsorption on the soils. Positive charge decrease on soil particles, concomitant proton consumption, and release of silicon (Si), sulfate (SO₄ ^2‐), and organic C were observed in selenite sorption by the soils. The development of surface particle negative charge with selenite sorption was smaller in the H₂O₂‐treated soil than in the original soils and was scarcely observed in the ignition‐treated soil. It can be assumed that the increase of negative charge by selenite sorption was attributed to new negative sites borne by released insoluble organic matter and negative charge development directly by selenite sorption was small.     

Effects of changes in pH, ionic strength, and sulphate concentration on the CEC of temperate acid forest soils

As the acidity of rain diminishes, changes in the pH, ionic strength, and ion activities of the soil solution will influence the charge characteristics of soil. We have investigated the response of cation exchange capacity (CEC) of three acid forest soils of variable charge to small changes in pH, ionic strength, and SO^2?₄ concentration. The variable charge for these temperate soils has the same significance as for tropical soils and those from volcanic ash. Maximum absolute increase in CEC on increasing pH by 0·2–0·5 units reached 5 cmol_c kg^-1 in O horizons. The increase in CEC on doubling ionic strength in EA and Bsh horizons of a Cambic Podzol was about half that amount, but relative gains compared to effective CEC were 65 and 46%, respectively. For other soil horizons, absolute changes were smaller, and relative changes were between 10 and 30%. Halving the SO^2?₄ concentration significantly influenced CEC only in some samples. Both pH and ionic strength must be adjusted with care when determining CEC_c of acid forest soils. Decreasing acid deposition will not inevitably increase CEC_c because in some soils pH effects may be balanced by simultaneous decrease in ionic strength.     

THE CONTENTS AND SORPTION OF CADMIUM IN SOME AGRICULTURAL SOILS OF ENGLAND AND WALES

Cadmium sorption was measured in 10 agricultural soils with pH ranging from 4.5 to 7.9, and total Cd content from 0.27 to 1.04 μg g^?1 dry soil. With initial Cd concentrations of 0.5 to 100.0 μM, sorption from 0.002 M CaCl₂ was described by the Freundlich adsorption equation but the gradients of the isotherms increased when the initial concentrations were below 0.5 μm. This indicates that there are specific sites of differing sorption energy; differences between soils in the gradients of the isotherms at low initial concentration could largely be accounted for by their contents of ‘free’ Fe₂O₃. When initial concentrations were below 0.5 μm there was a linear relationship between the quantity of Cd sorbed and the final concentration in solution. This relationship held with all soils except that of lowest pH from which there was a net loss of Cd to the solutions. Desorption was measured from three soils with contrasting pH. With the soil of lowest pH, over 80 per cent of sorbed Cd was desorbed to 0.002 m CaCl₂ and up to 30 per cent to 100 or 500 μm solutions of heavy metal chlorides. In contrast, only very small proportions (<1.25 per cent) were desorbed from the other soils with pH 6.7 and 7.8. The results indicate that Cd is strongly sorbed by soils of pH of above 6.0 when added in amounts comparable to additions in sewage sludges or phosphatic fertilizers, and illustrate the importance of liming as a means of reducing the mobility of this metal in soils.     

Ionic-strength and pH effects on the sorption of cadmium and the surface charge of soils

Two Oxisols (Mena and Malanda), a Xeralf and a Xerert from Australia and an Andept (Patua) and a Fragiaqualf (Tokomaru) from New Zealand were used to examine the effect of pH and ionic strength on the surface charge of soil and sorption of cadmium. Adsorption of Cd was measured using water, 0.01 mol dmp^?3 Ca(NO₃)₂, and various concentrations of NaNO₃ (0.01–1.5 mol dm^?3) as background solutions at a range of pH values (3–8). In all soils, the net surface charge decreased with an increase in pH. The pH at which the net surface charge was zero (point of net zero charge, PZC) differed between the soils. The PZC was higher for soils dominated by variable-charge components (Oxisols and Andept) than soils dominated by permanent charge (Xeralf, Xerert and Fragiaqualf). For all soils, the adsorption of Cd increased with an increase in pH and most of the variation in adsorption with pH was explained by the variation in negative surface charge. The effect of ionic strength on Cd adsorption varied between the soils and with the pH. In Oxisols, which are dominated by variable-charge components, there was a characteristic pH below which increasing ionic strength of NaNO₃ increased Cd adsorption and above which the reverse occurred. In all the soils in the normal pH range (i.e. pH>PZC), the adsorption of Cd always decreased with an increase in ionic strength irrespective of pH. If increasing ionic strength decreases cation adsorption, then the potential in the plane of adsorption is negative. Also, if increasing ionic strength increases adsorption below the PZC, then the potential in the plane of adsorption must be positive. These observations suggest that, depending upon the pH and PZC, Cd is adsorbed when potential in the plane of adsorption is either positive or negative providing evidence for both specific and non-specific adsorption of Cd. Adsorption of Cd was approximately doubled when Na rather than Ca was used as the index cation.     

EFFECTS OF IONIC STRENGTH ON CHEMISORPTION AND POTENTIAL-DETERMINING SORPTION OF PHOSPHATE BY SOILS

Amounts of inorganic phosphate (P) sorbed by two unfertilized soils, during times less than required to reach equilibrium, were affected by the ionic strength and cation species of the matrix solution. For non-equilibrium conditions the amounts of P sorbed increased with increasing ionic strength and were greater with Ca²⁺ than Na⁺. For higher P additions, resulting in equilibrium solution P concentrations greater than 30 to 40μrnole 1^?1, the effects of the matrix solution on P sorption were maintained at equilibrium, whereas at lower P additions the dependence of sorption on matrix solution composition was eliminated at equilibrium. Equilibrium sorption isotherms for each soil and matrix solution were described by three Langmuir equations, which corresponded to distinct concentration ranges or regions (I, II, and III) on the overall isotherm. The free energies of sorption (ΔG) for each region, were essentially independent of the soil matrix solution. The sorption maxima for regions I and II of the isotherm for a particular soil were also virtually independent of the matrix solution used. The sorption maximum for region III, however, was markedly dependent on the matrix solution, implying a potential-determining (p.d.) sorption mechanism.     

Degradation Kinetics of Perchlorate in Sediments and Soils

This study investigated the intrinsic perchlorate (ClO₄ ^-)degradation kinetics of sediments and soils from multiple sites in microcosm studies, including the influence of varying nitrate concentration (NO₃ ^--N from 1 to 22.8 ppm) and up to 300 ppm sulfate. The first-order degradation rates and lag times of both ClO₄ ^- and NO₃ ^- degradation were site-specific and dependent on environmental conditions such as organic substrate availability, nitrate, initial ClO₄ ^- concentration, and prior ClO₄ ^- exposure. At an initial ClO₄ ^- concentration of 5 ppm, ClO₄ ^- degradation rates ranged from 0.13 to 0.46 day^-1, and lag times of ClO₄ ^- degradation ranged from 0 to 60.0 days; while NO₃ ^- degradation occurred at rates ranging from 0.03 to 1.42 day^-1, with lag times ranging from 0 to 29.7 days. Under the same treatment conditions, NO₃ ^- degradation rates were relatively higher than that of ClO₄ ^-. Perchlorate degradation rates remained constant at both lower (0.5 ppm) and higher (5 ppm) ClO₄ ^- concentrations. Generally, ClO₄ ^- rates were affected by the availability of organic substrate, which was represented here by Total Volatile Solids (TVS) of sediments and soils, and not by NO₃ ^-. Nitrate did increase the lag time of ClO₄ ^- degradation, which may account for the persistence of ClO₄ ^- in the environment, especially when ClO₄ ^- is typically ppb levels in the environment compared to ppm levels of NO₃ ^-. This study showed rapid intrinsic ClO₄ ^- degradation in sediments and soils of contaminated sites, and highlighted the potential for natural attenuation of ClO₄ ^- in the environment.     

Partitioning of polycyclic aromatic hydrocarbons (PAH) to water-soluble soil organic matter

The mobility of polycyclic aromatic hydrocarbons (PAH) in soils can be influenced by the presence of dissolved organic matter. Partition coefficients of selected polycyclic aromatic hydrocarbons, ranging from 3-ring to 6-ring compounds, to water-soluble soil organic matter (WSSOM) were determined. Partition coefficients were determined for WSSOM obtained from two soils under agricultural use and forest and for commercially available humic acid (Aldrich), taking advantage of a reversed phase (C₁₈) separation method. The WSSOM was characterised with regard to charge and hydrophilic/hydrophobic properties with a dissolved organic matter (DOM) fractionation method. No sorption to WSSOM was found for the tri- and tetracyclic PAH, whereas the penta- and hexacyclic PAH showed a significant binding to both types of WSSOM and to Aldrich humic acid. The affinity of penta- and hexacyclic PAH to WSSOM was considerably lower compared to the affinity to Aldrich humic acid. This is suggested to be due to the lower amount of hydrophobic fractions, c. 30%, in the natural WSSOM as compared to Aldrich humic acid. Effective partition coefficients (Koc_eff) for the sorption of PAH to bulk soil calculated from K_DOC and DOM in the naturally occurring concentration range were only 60–70% of the K_oc values in pure water. The impact of DOM on pollutant transport is further influenced by non-equilibrium behaviour of PAH in soils and by sorption of DOM to the solid-soil matrix. Several scenarios are described in which the effect of DOM on pollutant transport may become important.     

RATIONALIZATION OF IONIC STRENGTH AND CATION EFFECTS ON PHOSPHATE SORPTION BY SOILS

The amounts of inorganic phosphate (P) sorbed by four contrasting unfertilized soils during 40 h were influenced by the ionic strength and cation species of the contacting solution (support medium) used, as indicated by isotherms over the final P concentration range of 0 to 1 μg P/ml and 0 to 10 μg P/ml. An increase in ionic strength enhanced P sorption during 40 h but the species of cation also influenced the amount of P sorbed, as shown by the isotherms obtained in 10^?2M Ca and 3 × 10^?2M Na systems. Although pH affected the amounts of P sorbed, pH effects alone could not adequately explain the differences in P sorption. Kinetic studies indicated that within the range of P addition used for each soil, the equilibrium P concentration, at infinite time, was independent of ionic strength and cation species. Consequently, the composition of the solution affected only the rate at which equilibrium was attained. The results are attributed to the effects of ionic strength on the surface charge of retaining components and the thickness of the diffuse double layer, and the effects of specilic sorption of a divalent cation on surface charge, as they relate to the rate of P sorption.     

Predicting phosphorus sorption isotherm parameters in soil using data of routine laboratory tests

Knowledge of phosphorus(P) sorption dynamics across different soil types could direct agronomic and environmental management of P. The objective of this study was to predict P isotherm parameters for a national soil population using data of routine laboratory tests. Langmuir and Freundlich sorption parameters were calculated from two different ranges(0–25 and 0–50 mg P L~(-1)) using an archive of representative agricultural soil types from Ireland.Multiple linear regression(MLR) identified labile forms of aluminium(Al) and iron(Fe), organic matter(OM), cation exchange capacity(CEC), and clay as significant drivers. Langmuir and Freundlich sorption capacities, Freundlich affinity constant, and Langmuir buffer capacity were predicted reliably, with R~2 of independent validation 0.9. Sorption isotherm parameters were predicted from P sorbed at a single concentration of 50 mg P L~(-1)(S_(50)). An MLR prediction of P sorption maximum in the 0–50 mg P L~(-1) range was achieved, to an accurate standard, using S_(50), OM, and Mehlich-3 Fe(R~2 of independent calibration and validation being 0.91 and 0.95, respectively). Using Giles' four shapes of isotherms(C, L, H, and S), L non-strict-and C-shaped isotherm curves accounted for 64% and 27% of the soils, respectively. Hierarchical clustering identified a separation of isotherm curves influenced by two ranges of Mehlich-3 Al. Soils with a low range of Mehlich-3 Al(2.5–698 mg kg~(-1)) had no incidence of rapid sorption(C shape). Single point indices, Al, or available soil data make the regression approach a feasible way of predicting Langmuir parameters that could be included with standard agronomic soil P testing.     

Interactions of allophane with humic acid and cations

Allophanic soils are known to accumulate organic matter, but the underlying mechanism is not well understood. Here we have investigated the sorption of humic acid (HA) by an allophanic clay in the presence of varied concentrations of either CaCl₂ or NaCl as background electrolytes. Both the HA and the clay were separated from New Zealand soils. Much more HA was sorbed in CaCl₂ than in NaCl of the same ionic strength. Apparently Ca²⁺ ions were more effective than Na⁺ ions in screening the negative charge on HA. In CaCl₂ the HA molecule might also assume a more compact configuration than in NaCl. In the presence of CaCl₂ sorption increased, reached a maximum, and then declined as the concentration of HA in solution was increased. This behaviour was not observed in NaCl where sorption showed a gradual and steady increase with HA concentration. We propose that ligand exchange occurs between the surface hydroxyl groups of allophane and the carboxylate groups of HA. As a result, the allophane–HA complex acquires negative charges, requiring the co‐sorption of extraneous cations (Ca²⁺ or Na⁺) for charge balance. The Ca²⁺ co‐sorbed can attract more HA to the complex possibly by a cation‐bridging mechanism, giving rise to a maximum in sorption. The decline in sorption beyond the maximum may be ascribed to a decrease in the concentration of free Ca²⁺ ions through binding to HA molecules in solution. The increase in supernatant pH may be attributed to a ligand exchange reaction between the surface hydroxyls of allophane and the carboxylate groups of HA, and proton binding to the allophane–HA complex.     

Einfluss eisenhaltiger Klärschlämme auf Kenngrößen der P‐Verfügbarkeit in Ackerböden

Influence of iron content in sewage sludges on parameters of phosphate availability in arable soils The use of iron salts for the P elimination in sewage plants is widely used. But it is not clear whether the P availability in arable soils is negatively influenced by iron compounds or not. The aim of the investigations was, therefore, to study the influence of two sewage sludges with a high and a low Fe content respectively on P sorption and phosphate concentration (P_i) in the soil solution after application of CaHPO₄ or sewage sludge to 5 loamy and 4 sandy soils (pot experiments and 1 silty loam (field experiment)). Soils were analyzed 1, 6, and 13 months after P application. Sludge Gö contained 12 kg P and 65 kg Fe (t DM)^—1 (P : Fe = 1 : 5.4) and sludge Sh 25 kg P and 39 kg Fe (t DM)^—1 (P : Fe = 1 : 1.5). The basic P application was 60 kg P ha^—1 (= 30 mg P (kg soil)^—1 in the pot experiment, as sludge or as CaHPO₄). P uptake by maize was determined in a separate pot experiment with a loamy soil and the same P application rate. The P sorption capacity remained similar in all soils after application of sludge Sh (P : Fe = 1:1.5) compared with soils without sludge, however, after application of sludge Gö the P sorption increased by 16% (0—59%). After application of sludge Sh the mean P_i concentration increased in loamy soils by 34% and in sandy soils by 15%. On the other hand the P_i concentration decreased after applying sludge Gö by 13% and 36% as compared to the controls of the respective soils. In the field experiment the P_i concentration of plots with a high P level (50 mg lactate soluble P (kg soil)^—1) was also significantly decreased after application of 10 t sludge Gö (126 kg P ha^—1) in comparison with triple phosphate. One month after the application of increasing amounts of sludge Gö (5, 10, 15 t DM ha^—1) both the concentration of oxalate‐soluble Fe in the soil and the P sorption were increased. The elevated relationship between these two parameters was highly significant (r² = 0.6 — 0.97). Plant uptake of P was less after application of sludge Gö than after application of sludge Sh and much less than P uptake from CaHPO₄. Sewage sludges with a P : Fe ratio of 1 : 5 should not be recommended for agricultural use, as the P availability is significantly reduced. Iron salts should not be used for conditioning of sludges.     

Cadmium soil sorption at low concentrations: I. Effect of time,cadmium load,pH, and calcium

Sorption of Cd at low concentrations onto two Danish soils (loamy sand, sandy loam) was examined in terms of kinetics and governing factors. From an environmental point of view soil sorption of Cd is a fast process: More than 95% of the sorption takes place within 10 min, equilibrium is reached in 1 hr, and exposures up to 67 wk did not reveal any long term changes in Cd sorption capacities. The soils have very high affinity for Cd at pH = 6.00 (10^?3 M CaCl₂) exhibiting distribution coefficients in the order of 200 to 250 (soil Cd concentration/solute Cd concentration). However, the sorption isotherms describing the distribution of Cd between soil and solute are slightly curvelinear. In the pH-interval 4 to 7.7, the sorption capacity of the soil approximately increases 3 times for a pH increase of one unit. Increasing the Ca concentration from 10^?3 to 10^?2 M reduces the sorption capacity of the sandy loam to one third.     

几种有机酸对可变电荷和恒电荷土壤吸附镉的影响

The objectives of this study were to illustrate the reaction processes, to identify and quantify the precipitates formed, and to estimate the porosity losses in order to eliminate drawbacks during remediating monochlorobenzene （MCB） and trichloroethylene （TCE）-contaminated aquifers using the ORC-GAC-Fe^0-CaCO3 system. The system consisted of four columns （112 cm long and 10 cm in diameter） with oxygen-releasing compound （ORC）, granular activated carbon （GAC）, zero-valent iron （Fe^0）, and calcite used sequentially as the reactive media. The concentrations of MCB in the GAC column effluent and TCE in the Fe^0 column effluent were below the detection limit. However, the concentrations of MCB and TCE in the final calcite column exceeded the maximum contaminant level （MCL） under the Safe Drinking Water Act of the US Environmental Protection Agency （US EPA） that protects human health and environment. These results suggested that partitioning of MCB and TCE into the gas phase could occur, and also that transportation of volatile organic pollutants in the gas phase was important. Three main precipitates formed in the ORC-GAC-Fe^0-CaCO3 system： CaCO3 in the ORC column along with Fe（OH）2 and FeCO3 in the Fe^0 column. The total porosity losses caused by mineral precipitation corresponded to about 0.24% porosity in the ORC column, and 1% in the Fe^0 column. The most important cause of porosity losses was anaerobic corrosion of iron. The porosity losses caused by gas because of the production and entrapment of oxygen in the ORC column and hydrogen in the Fe^0 column should not be ignored. Volatilization, precipitation and porosity losses were considered to be the main drawbacks of the ORC-GAC-Fe^0-CaCO3 system in remediating the MCB and TCE-contaminated aquifers. Thus, measurements such as using a suitable oxygen-releasing compound, weakening the increase in pH using a buffer material such as soil, stimulating biodegradation rates and minimizing the plugging caused by the relatively high dissolved oxygen levels should be taken to eliminate the drawbacks and to improve the efficiency of the ORC-GAC-Fe^0-CaCO3 system.     

Specific sorption of trace amounts of cadmium by soils

Abstract

Sorption of trace quantities of Cd in four soils of different chemical and mineralogical properties, was studied. Initial Cd concentrations were between 15 to 150 μg. 1^?1. The sorption isotherms were linear and had a positive intercept in three of the soils, indicating a constant partition‐high affinity sorption isotherm (Giles et. al⁶). The data also followed the Freundlich sorption isotherm, and the Freundlich K parameter was taken as a measure of the relative affinity of the different soils for the Cd metal sorbed. Cadmium sorbed was extracted by IN‐NH₄C1 followed by 0.1N HC1, and the fraction remaining in the soils was considered specifically sorbed Cd. This fraction also followed a linear sorption isotherm, and was around 30% for the four soils studied. The sorption order for the amount of specifically sorbed Cd showed that the Boomer soil (kaolinite‐iron oxides) had the lowest affinity for specific sorption of this metal. This was taken as evidence that kaolinite and iron oxides have a lower capacity for retaining cadmium through specific sorption mechanism(s) than the materials present on the other soils (2:1 layer silicates and humic substances). The existence of specific mecha‐nism(s) responsible by the sorption of trace quantities of Cd in soil solutions has important implications on soil‐plant relationships, Cd mobility in soil profiles and control of Cd activity in soil solutions.     

Nickel adsorption in two Oxisols and an Alfisol as affected by pH,nature of the electrolyte,and ionic strength of soil solution

Background, aim, and scope  The retention of potentially toxic metals in highly weathered soils can follow different pathways that variably affect their mobility and availability in the soil–water–plant system. This study aimed to evaluate the effects of pH, nature of electrolyte, and ionic strength of the solution on nickel (Ni) adsorption by two acric Oxisols and a less weathered Alfisol. Materials and methods  The effect of pH on Ni adsorption was evaluated in surface and subsurface samples from a clayey textured Anionic ‘Rhodic’ Acrudox (RA), a sandy-clayey textured Anionic ‘Xantic’ Acrudox (XA), and a heavy clayey textured Rhodic Kandiudalf (RK). All soil samples were equilibrated with the same concentration of Ni solution (5.0 mg L⁻¹) and two electrolyte solutions (CaCl₂ or NaCl) with different ionic strengths (IS) (1.0, 0.1 and 0.01 mol L⁻¹). The pH of each sample set varied from 3 to 10 in order to obtain sorption envelopes. Results and discussion  Ni adsorption increased as the pH increased, reaching its maximum of nearly pH 6. The adsorption was highest in Alfisol, followed by RA and XA. Competition between Ni²⁺ and Ca²⁺ was higher than that between Ni²⁺ and Na⁺ in all soil samples, as shown by the higher percentage of Ni adsorption at pH 5. At pH values below the intersection point of the three ionic strength curves (zero point of salt effect), Ni adsorption was generally higher in the more concentrated solution (highest IS), probably due to the neutralization of positive charges of soil colloids by Cl⁻ ions and consequent adsorption of Ni²⁺. Above this point, Ni adsorption was higher in the more diluted solution (lowest ionic strength), due to the higher negative potential at the colloid surfaces and the lower ionic competition for exchange sites in soil colloids. Conclusions  The effect of ionic strength was lower in the Oxisols than in the Alfisol. The main mechanism that controlled Ni adsorption in the soils was the ionic exchange, since the adsorption of ionic species varied according to the variation of pH values. The ionic competition revealed the importance of electrolyte composition and ionic strength on Ni adsorption in soils from the humid tropics. Recommendations and perspectives  The presence of NaCl or CaCl₂ in different ionic strengths affects the availability of heavy metals in contaminated soils. Therefore, the study of heavy metal dynamics in highly weathered soils must consider this behavior, especially in soils with large amounts of acric components.     

应用XAFS研究草酸根和胡敏酸对As(V)在红壤中吸附的影响

结合吸附实验和X光吸收精细结构光谱(XAFS)分析,研究了草酸根和胡敏酸对As(V)在红壤中吸附的影响,分析了As(V)在红壤中的化学形态和微观结构以及草酸根、胡敏酸的影响特征。结果表明,当pH6.0时,红壤主要是通过基团交换反应吸附As(V),草酸根和胡敏酸可以通过竞争吸附位点抑制红壤中As(V)的吸附,其抑制作用随浓度增大而增强。XAFS光谱学数据表明,红壤中吸附的砷以+5价态存在,主要与铁铝矿物形成以约0.317 nm As-Al和0.328 nm As-Fe原子间距为特征的双齿双核结构的内层复合物,复合物结构类型不受砷浓度和草酸根、胡敏酸的影响。     

Extraction with 0.01 m CaCl2 underestimates the concentration of phosphorus in the soil solution

The aim of this paper was to compare the concentration of P in soil extracts prepared with water and a ‘soil solution proxy’ (‘SSP’, that is, a salt solution similar in ionic composition and strength to the actual soil solution) with that in 0.01 m CaCl₂ extracts, which is usually taken as a measure of soil P intensity. Seventy widely ranging agricultural soils from the Mediterranean part of Spain were used. Soil/solution ratio was 1:10 and extraction time 3 days. For 0.01 m CaCl₂, a short extraction time of 30 min was also used as the reference method. CaCl₂‐P(3 days) and CaCl₂‐P(30 min) were not significantly different for the 40 noncalcareous soils group, but CaCl₂‐P(3 days) was significantly larger than CaCl₂‐P(30 min) for the 30 calcareous soils group. The Water‐P/CaCl₂‐P(30 min) ratio was not significantly related to any soil property, its mean being 6.3 for the noncalcareous and 5.8 for the calcareous soils group. The mean SSP‐P/CaCl₂‐P(30 min) ratio was 2.6 for the noncalcareous and 3.1 for the calcareous soils group, and decreased slightly with increasing ionic strength of the soil solution in the noncalcareous soils group. These results are consistent with the promoting influence of the Ca ion and ionic strength on P adsorption by permanent‐charge soils. The fact that extraction with 0.01 m CaCl₂ generally results in underestimation of the actual concentration of P in the soil solution should be considered when CaCl₂‐P is used as a soil P test.     

Predicting mobility of alkylimidazolium ionic liquids in soils

Background, aim, and scope  Ionic liquids (ILs) are a new class of alternative solvents that make ideal non-volatile media for a variety of industrial processes such as organic synthesis and biocatalysis, as alternative electrolytes, as phases and phase modifications in separation techniques, and as alternative lubricants. Once the large-scale implementation of ILs begins, the industrial application will follow. In view of their great stability, they could slip through classical treatment systems to become persistent components of the environment, where the long-term consequences of their presence are still unknown. Sorption on soils has a critical effect on the transport, reactivity, and bioavailability of organic compounds in the environment. So far, the IL sorption mechanism was investigated solely on the basis of batch experiments, which precluded any assessment of the dynamics of the process. An understanding of the mobility of ILs in soil columns is crucial for an accurate prediction of their fate in the soil. The aim of this study therefore was to investigate in detail the mobility of selected imidazolium ILs on three soil types. Moreover, it was decided to study these processes in soils from the coastal region (Gdańsk, Poland), which usually constitute a very important geochemical compartment, participating in the transport of contaminants on their way to the sea. Materials and methods  The mobility of alkylimidazolium ILs was investigated in columns containing soils from the coastal area. In addition, the sorption processes in all the soil systems studied were described isothermally and the equilibrium sorption coefficient was evaluated. The sorption capacities were determined according to OECD guidelines. Sorption dynamics was studied with use of polypropylene columns (diameter—10 mm, height—100 mm) packed with 10 g of soil. The ionic liquid solution was then injected into the soil column and left for 24 h to equilibrate. After this, a solution of 0.01 mM CaCl₂ was pumped through the column at a rate of 0.3 ml min^–1. Effluents were collected from the bottom of the column and analyzed by HPLC. Results  Sorption was strongest on the Miocene silt and the alluvial agricultural soil and weakest on the podsolic soil and Warthanian glacial till. The K _d value of long-chain ILs was far higher than that of the short-chain ones. Among the substances tested, hydroxylated ILs were usually more weakly sorbed. Desorption of ILs is inversely correlated with sorption intensity. The experimental results of the column tests correlate well with those from batch experiments. In the cases of weakly binding soils, ILs were detected almost immediately in the eluent. The elution profiles of long-chain ILs indicate that these compounds are very strongly sorbed onto most soils, although certain amounts were transported through the soil. ILs exhibit a certain mobility in soils: in particular, salts with short and/or hydroxylated side chains are extremely mobile. Discussion  The results indicate a stronger binding of ILs in the first sorption layer; once the first layer is saturated, there are no more active sites on the soil surface (no free charged groups); hence, there are no more strong electrostatic binding sites, and dispersive interaction becomes the dominant interaction potential. The influence of the structure of the ILs, especially the side-chain length was also confirmed: The K _d value of long-chain ILs was far higher than that of the short-chain ones. The long alkyl side chain facilitates dispersive interactions with soil organic matter and intermolecular binding, and the build-up of a second layer becomes possible. Among the substances tested, hydroxylated ILs were usually more weakly sorbed. The hydroxyl group in the side chain can alter the polarity of the compound so strongly that interaction with organic matter hardly occurs; these salts then remain in the aqueous phase. The experimental results from the column tests correlate well with those from batch tests. In the weakly binding soils (with low organic matter), the only binding to the soil surface must be via electrostatic interactions, although intermolecular van der Waals (ionic liquid–ionic liquid) interactions could also be taking place. The elution profile maxima for organic rich soils are far smaller than for the other soils. In the former, hydrogen bonding, dispersive and π…π interactions play a more important part than electrostatic interactions. The rapidly “disappearing” maxima of the elution peaks may indicate that, after elution of ILs from the second layer, it is difficult to extract further sorbed ILs. In the first layer, the ILs are bound by much stronger electrostatic interactions. To break these bonds, a greater energy is required than that sufficient to extract ILs from double sorption layers. Results indicate, moreover, that hydrophobic ILs will be sorbed in the first few centimeters of the soil; migration into the soil will therefore be almost negligible. Conclusions  Sorption of ILs was the strongest in soils with the highest cation exchange capacities and a high organic content. ILs were also more strongly bound to the first sorption layer. The sorption coefficients of long-chain ILs were far higher than those of short-chain ones; usually, hydroxylated derivatives were the least strongly sorbed. Results of soil column experiments to investigate the mobility of ILs in soils correlated well with those from batch tests, and the elution profiles were also well correlated with organic matter content. The observed rapidly disappearing elution peak maxima probably indicate that, after elution of the ILs from the second layer, it is difficult to extract further sorbed compounds. Recommendations and perspectives  Obtained results gave an interesting insight into mobility of ionic liquids in soil columns. However, several questions are now opened. It is therefore necessary to undertake further studies focused on total cycle of ionic liquids in the soil environment. This should include their evapotrasporation (lysimeter test), bioaccumulation by plants as well as degradation and transformation processes (chemical, biological, and physical) typically occurring in soils. Moreover, a further risk assessment of ILs is desirable since this study has indicated that these compounds, especially those with low lipophilicities, are generally mobile in the soil matrix. It is already known that short-chain ILs are characterized by low toxicities; should they enter the environment, they will probably migrate within the soil and pose a risk of contamination of surface and ground waters. This topic is relevant to the audience. Environmental threat of short-chain ionic liquids is currently unknown. From the predictive point of view, judging on known low acute toxic effects or high polarities of these compounds seems to be not enough to confirm their “environmental friendliness”. If we are to fully understand the potential environmental effects, one should also have an insight into long-term biological consequences of these ionic liquids, including chronic toxicity tests, bioaccumulation, and biotransformation rates as well as stability against natural elimination mechanisms.