几种吸附剂对阿特拉津的吸附及其 Zeta 电位特性研究

通过振荡吸附平衡试验,研究了蒙脱石、凹凸棒石、竹炭、木炭对阿特拉津的吸附行为,讨论了pH值、离子强度对吸附的影响,并考察了吸附剂表面的Zeta电位变化。结果表明,几种吸附剂对阿特拉津的吸附均符合Freundlich方程;竹炭、木炭的吸附能力明显高于蒙脱石和凹凸棒石。吸附剂对阿特拉津的吸附量随着悬液离子强度的增加而增加,在悬液pH一定(pH=6),离子强度为10-3mol/L NaNO3时,蒙脱石、凹凸棒石对阿特拉津的吸附量分别为538.30、609.68 mg/kg,当离子强度增加为10-2mol/L时,吸附量分别增至611.26、731.63 mg/kg;当离子强度由10-3增至10-1mol/L NaNO3时,竹炭、木炭对阿特拉津的吸附量有较多增加。当悬液pH在3~8范围时,几种吸附剂表面均带负电荷,其Zeta电位值随着pH的增加而增加,随离子强度的增加而减小。悬液离子强度一定时,随着pH的增加,吸附阿特拉津后吸附剂表面Zeta电位变化不显著。研究结果有助于从机理上解析吸附剂对有机污染物的吸附行为。     

Adsorption of atrazine and metolachlor in three soils from Blue Creek wetlands, Waterville, Ohio

Atrazine and metolachlor are extensively used pesticides in agricultural activities in northwest Ohio. Adsorption coefficients are often used to model pesticide fate and transport. Many physical-chemical parameters, such as organic matter, clay content, pH, and ionic strength, affect pesticide adsorption. Adsorption kinetics and adsorption isotherms were studied by batch experiment. Effects of humic acid, solution pH, and ionic strength on atrazine and metolachlor adsorption were also approached. After 24 h, both atrazine and metolachlor reached adsorption equilibrium in three local soils. Adsorption isotherms were described by Freundlich equations. The Freundlich coefficient (Kf) ranged from 0.14 to 4.47 (L kg^–1) for atrazine, and 0.04 to 5.30 (L kg^–1) for metolachlor. Adsorption capacity decreased in the order Sloan loam > Del Rey loam > Ottokee fine sand. Koc values varied considerably for both pesticides: metolachlor > in Sloan loam, atrazine metolachlor in Del Rey loam, and atrazine > metolachlor in Ottokee fine sand. In addition to organic matter content, clay played a key role in adsorption in the Del Rey loam and Ottokee fine sand. Higher adsorption was observed at pH 5 for both pesticides. As pH decreased to 3 and increased to 11, adsorption decreased. Adsorption increased as ionic strength increased.     

Removal of Cu2+ and Cd2+ from Aqueous Solution by Bentonite Clay Modified with Binary Mixture of Goethite and Humic Acid

Pre-modification of bentonite clay with goethite, humic acid, and a binary mixture of goethite and humic acid reagents increased its cation exchange capacity from 95 to 105.32, 120.4, and 125.8 meq/100 g of bentonite clay, respectively. The effective pre-modification of bentonite clay with goethite, humic acid, and goethite–humic acid reagents was confirmed from their Fourier transform infrared spectra which suggested that modification was effective on the AlAlOH and Si–O sites for goethite and humic acid modification and AlAlOH for goethite–humic acid modification. The presence of 0.001 M NaNO₃ electrolyte increased the adsorption capacity of bentonite clay. Temperature was observed to favor the adsorption of Cu²⁺ and Cd²⁺ onto both the raw and modified bentonite clay samples. The goethite–humic acid-modified bentonite gave the best adsorption capacity of ≈10 and 16 mg/g at 30 and 50°C, respectively, for both metal ions. The inner sphere complexation mechanism was suggested for the adsorption of both metal ions onto the modified adsorbents. Modifying bentonite clay with a binary mixture of goethite and humic acid reduced the selectivity of bentonite clay for either Cu²⁺ or Cd²⁺. Preadsorbed goethite and humic acid on bentonite clay will further reduce the mobility of heavy metal ions in soils and in aquatic environments.     

Ionic strength effects on surface charge and adsorption of phosphate and sulphate by soils

Two surface soils (Patua and Tokomaru) of contrasting mineralogy were incubated with several levels of either CaCO₃ or HC1. The effects of ionic strength on pH, on surface charge, and on the adsorption of phosphate and sulphate were measured in three concentrations of NaCl. The pH at which the net surface charge was zero (point of net zero charge—PZC) was 1.8 for the Tokomaru soil and 4.6 for the Patua soil: differences that can be related to mineralogical composition. There was an analogous point of zero salt effect (PZSE) that occurred at pH 2.8 for the Tokomaru soil and at 4.6 for the Patua soil. The presence of permanent negative charge in the Tokomaru soil resulted in an increase in PZSE over PZC. The effect of ionic strength on adsorption varied greatly between phosphate and sulphate. For phosphate, there was a characteristic pH above which increasing ionic strength increased adsorption and below which the reverse occurred. This pH (PZSE for adsorption) was higher than the PZC of the soil and was 4.1 for the Tokomaru soil and 5.3 for the Patua soil. In contrast, increasing ionic strength always decreased sulphate adsorption and the adsorption curves obtained in solutions of different ionic strengths converged above pH 7.0. If increasing ionic strength decreases adsorption, the potential in the plane of adsorption must be positive. Also, if increasing ionic strength increases adsorption, the potential must be negative. This suggests that, depending upon pH, phosphate is adsorbed when the potential in the plane of adsorption is either positive or negative, whereas sulphate is absorbed only when the potential is positive.     

Invasive Freshwater Macrophyte Alligator Weed: Novel Adsorbent for Removal of Malachite Green from Aqueous Solution

The batch sorption experiments were carried out using a novel adsorbent, freshwater macrophyte alligator weed, for the removal of basic dye malachite green from aqueous solution. Effects of process parameters such as initial solution pH, contact time, adsorbent concentration, particle size, and ion strength were investigated. The adsorbent was characterized by FT-IR. The adsorption of malachite green by alligator weed was solution pH dependent. The adsorption reached equilibrium at 240 min for two particle size fractions. The pseudo-first-order equation, Ritchie second-order equation, and intraparticle diffusion models were tested. The results showed that adsorption of malachite green onto alligator weed followed the Ritchie second-order equation very well and the intraparticle diffusion played important roles in the adsorption process. The Langmuir and Freundlich equations were applied to the data related to the adsorption isotherms and the observed maximum adsorption capacity (q _max) was 185.54 mg g^?1 at 20°C according to the Langmuir model. The effects of particle size, adsorbent concentration, and ionic strength on the malachite green adsorption were very marked. The alligator weed could serve as low-cost adsorbents for removing malachite green from aqueous solution.     

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.     

Glyphosate adsorption on synthetic allophanes and halloysite: Effects of pH and mineral properties

Background

Glyphosate (GLP) is a widely used herbicide with possible adverse effects on human health and the environment. In soils, GLP strongly adsorbs on clay-sized minerals, depending on pH, the amount of organic carbon, as well as the contents and properties of Al and Fe oxyhydroxides and clay minerals. Many clay-sized minerals have already been investigated regarding GLP adsorption behavior, but information on minerals commonly found in volcanic soils is still lacking.

Aim

The aim of this study was to investigate for the first time the pH-dependent adsorption of GLP on allophane and halloysite, typical minerals found in volcanic soils.

Methods

GLP adsorption was studied in batch experiments at three pH values (5, 6, and 7). Synthetic allophanes with two different initial Al:Si ratios (1.4 and 1.8) and a halloysite were used as adsorbents.

Results

The adsorption capacity (AC) increased with rising Al:Si ratio and decreasing pH. The AC of allophane was significantly higher than that of halloysite. GLP adsorption on allophane was larger than that reported for other clay minerals and Al and Fe oxyhydroxides, especially at low pH. The AC of halloysite was higher than reported for most other clay minerals.

Conclusion

Different mineral formation pathways in volcanic soils, notably the formation of halloysite versus allophanes, strongly affect the soils’ retention capacity for GLP. The high AC of allophanes may induce the low mobility of GLP in allophane-containing soils. Long-term use of GLP may accumulate the herbicide in these soils with potential effects on biodiversity and ecosystem services.     

Reduction of ochratoxin a levels in red wine by bentonite, modified bentonites, and chitosan

Adsorption method may play an important role to remove ochratoxin A (OTA) from wine by bentonite (B), nonylammonium bentonite (NB), dodecylammonium bentonite (DB), KSF-montmorillonite (KSF), and chitosan bead (CB). The optimum conditions of OTA adsorption from synthetic solutions were revealed at room temperature and pH 3.5. The adsorption equilibria of B and NB were almost established within 120 and 240 min, respectively. DB, KSF, and CB had about 90 min of equilibration time. The adsorption efficiency carried out in the synthetic OTA solution did not change remarkably when the amounts of adsorbents were 25 mg for bentonite, DB, and KSF and 100 mg for NB and CB. Furthermore, 25 mg of adsorbents was used at all adsorption studies in synthetic solution. The adsorption isotherm was fitted with mostly a Freundlich equation with respect to the correlation coefficients. The adsorption data were evaluated using Langmuir and Freundlich equations having Kf values ranging from 0.011 to 9.5 with respect to correlation coefficients (R2 = 0.900-0.977). DB and KSF have the highest adsorption capacity for OTA in synthetic solutions. In wine, the removal of OTA was succeeded at a percentage of 60-100 by KSF and CB. Furthermore, the highest adsorption capacity of OTA for red wine was obtained by using 250 mg of KSF, which caused less damage to the nature of wine and also low adsorption of polyphenols and anthcyans.     

Equilibrium studies for the adsorption of dyestuffs from aqueous solutions by low-cost materials

A number of low-cost materials (teakwood bark, ricehusk, coal, bentonite clay, hair and cotton waste) have been used as adsorbents for dyestuffs in aqueous solutions. Four red and four blue dyes have been studied; each color group consisted of an acidic, a basic, a disperse and a direct dye. The equilibrium isotherm for each dye-adsorbent system was determined and adsorption capacities from zero to 200 mg dye g^?1 of adsorbent was obtained. In general basic dyes adsorbed to a greater extent than the other dye classes but no single characteristic of the dye or adsorbent seemed responsible for such dye-adsorbent interactions and adsorption capacities.     

The effect of pH on the retention of Cu,Pb, Zu and Cd by clay-humic acid mixtures

The amount of metal ion sorbed by the solids increased with increasing pH over the range 3 to 6, and with mixtures of clay-cellulose or illite-humic acid the uptake corresponded to the direct addition of individual substrate adsorption values. When the humic acid samples were admixed with Na⁺-form kaolinite or montmorillonite, there was some reduction in adsorption, attributable to component interactions, and this effect was most marked in the presence of Cu and Zn ions. In alkaline media there was competition between the ability of the organic material to form soluble metal humates and the tendency of the clays to strongly retain the sparingly soluble metal hydroxy species formed at pH > 6. In most systems studied retention by the solid phase predominated. In the presence of tannic acid there were distinct pH regions in which the four metal ions formed compounds of limited solubility, with the pH for maximum precipitation ranging from 4.5 (Cu) to 7 (Cd). The introduction of clay suspensions increased the amount precipitated/sorbed in these pH regions. The amount of Cu, Pb, Zn or Cd retained by mixed suspensions varied markedly with pH, nature of the clay and the chemical nature of organic components.     

Phosphate adsorption on uncoated and humic acid-coated iron oxides

Purpose

The phosphate adsorption on natural adsorbents is of particular importance in regulating the transport and bioavailability of phosphates in environmental system. In soils, oxides are often associated with organic matter and form mineral-organic complexes. The aim of the present paper was to investigate the mechanisms of phosphate adsorption on these complexes.

Materials and methods

Phosphate adsorption on uncoated and humic acid (HA)-coated iron oxide complexes was investigated at different ionic strengths and pH by isotherm experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy.

Results and discussion

Results showed that HA-coated iron oxide complexes caused a decrease in the specific surface area (SSA) and the isoelectric point (IEP) of oxides. Phosphate adsorption on iron oxides was insensitive to changes of ionic strength, while it increased on the complexes with increasing ionic strength. The presence of HA decreased the maximum adsorption and the affinity of phosphate on the complexes. The zeta potential of phosphate-bound iron oxides linearly reduced with the increment of phosphate surface coverage, while the zeta potential of complexes with adsorbed phosphate kept at the same level. ATR-FTIR analysis suggested the formation of phosphate-metal complexation. The presence of HA promotes the formation of the monodentate phosphate complexes at pH 4.5 and significantly influenced phosphate species at pH 8.5.

Conclusions

The amount of phosphate adsorbed was reduced, and the phosphate speciation was also influenced when phosphate was adsorbed on HA-coated iron oxide complexes compared with phosphate adsorption on pure goethite and hematite.

     

THE ADSORPTION OF COPPER BY SOIL MATERIALS AT LOW EQUILIBRIUM SOLUTION CONCENTRATIONS

The adsorption of copper by individual soil components (organic matter fractions, oxides and clay minerals) was examined at equilibrium solution concentrations of copper within the range found in natural soils, the distribution of copper between solution and solid phases being measured by means of labelling with radioactive ⁶⁴Cu. At these low solution concentrations it was found that the copper adsorption isotherms were essentially linear. The oxides and organic materials adsorbed the greatest amounts of copper. The concentration of copper in natural soil solutions will be controlled by these materials to a far greater extent than by the clay minerals, the influence of which may be negligible in some soils. Solution concentrations of copper are relatively unaffected by both the background concentration of major cations and by changes in pH within the ionic strength and pH range found in normal agricultural soils. Copper adsorption studies with humic and fulvic acids showed that total solution copper concentrations could be greatly enhanced above the equilibrium levels for ionic copper by the presence of soluble organic complexes. The importance of taking into account the presence of such copper complexes in soil copper studies is emphasised.     

土壤胶体对蛋白质的吸附

土壤有机-无机复合体是土壤肥力的物质基础之一,不仅依随成土过程而发生变化,人类耕作利用也可产生影响。     

支持电解质浓度对磷酸根在可变电荷土壤表面吸附和解吸的影响

研究了离子强度对2种可变电荷土壤中磷酸根吸附和解吸的影响。结果表明,当pH分别大于3.7和4.0时,红壤和砖红壤对磷酸根的吸附量随离子强度的增加而增加;当pH分别小于3.7和4.0时,红壤和砖红壤对磷酸根的吸附量随离子强度呈相反的变化趋势。电解质主要通过改变离子专性吸附面上的电位来影响磷酸根的吸附。Zeta电位的测定结果表明,当pH大于土壤胶体的等电点(IEP)时,吸附面上电位为负值,且随离子强度增加数值减小,对磷酸根的排斥力减小,土壤表面对磷酸根的吸附量增加;当pH小于IEP时,吸附面上的电位为正值,它随离子强度增加而减小,不利于磷酸根的吸附。解吸实验的结果表明,吸附于可变电荷土壤表面的磷酸根在去离子水中的解吸量高于0.1 mol L-1NaNO3体系中的解吸量。这同样由于电解质浓度对土壤表面吸附面上的电位的影响所致。     

Die Veränderung der Phosphatintensität der Bodenlösung eines Pelosol-Pseudogleys nach Grünlandumbruch

Long-term change in phosphate intensity in a clay soil after turning grassland into arable land In a 7years field experiment on a poorly drained clay (Pelosol-Pseudogley) after turning permanent grassland into arable land, the phosphate concentration in the soil solution (P_l) decreased and P retention (P_s) increased even if as much as 265 kg P ha^?1 was added in excess of plant uptake. Neither loss in organic matter nor disaggregation of the well aggregated grassland soil by soil management seemed to be responsible for this decrease in P_l. Instead, a slight increase in pH within the 7 years and, to a lesser extent, a concomitant increase in exchangeable Ca are assumed to have caused the decrease in P_l. Laboratory experiments in which pH, exchangeable Ca and ionic strength were varied support the field results. A multiple correlation between P_l and pH plus exchangeable Ca explained 89% of the variation of P_l whereas pH and Ca alone explained only 76 and 42%, respectively. Solubility data placed the solutions around the hydroxyapatite (HA) isotherm even when P-fertilizer were added in excess of plant uptake. It seems unlikely, therefore that HA governs P_l in this soil. Instead, the results are in favour of surface P adsorption to determine P_l. The effect of exchangeable Ca and ionic strength is then explained by their effects on the thickness of the electric double layer which in turn influences P adsorption.     

Formulation engineering can improve the interfacial and foaming properties of soy globulins

In this contribution, we have analyzed the effect of different strategies, such as change of pH (5 or 7) or ionic strength (at 0.05 and 0.5 M), and addition of sucrose (at 1 M) and Tween 20 (at 1 x 10(-4) M) on interfacial characteristics (adsorption, structure, dynamics of adsorption, and surface dilatational properties) and foam properties (foam capacity and stability) of soy globulins (7S and 11S at 0.1 wt %). We have observed that (1) the adsorption (presence of a lag period, diffusion, and penetration at the air-water interface) of soy globulins depends on the modification in the 11S/7S ratio and on the level of association/dissociation of these proteins by varying the pH and ionic strength (I), the effect of sucrose on the unfolding of the protein, and the competitive adsorption between protein and Tween 20 in the aqueous phase. The rate of adsorption increases at pH 7, at high ionic strength, and in the presence of sucrose. (2) The surface dilatational properties reflect the fact that soy globulin adsorbed films exhibit viscoelastic behavior but do not have the capacity to form a gel-like elastic film. The surface dilatational modulus increases at pH 7 and at high ionic strength but decreases with the addition of sucrose or Tween 20 into the aqueous phase. (3) The rate of adsorption and surface dilatational properties (surface dilatational modulus and phase angle) during adsorption at the air-water interface plays an important role in the formation of foams generated from aqueous solutions of soy globulins. However, the dynamic surface pressure and dilatational modulus are not enough to explain the stability of the foam.     

~(137)Cs在水-吸附剂体系中的行为

吸附剂对水体中1 37Cs的吸附随着时间延长而增加 ,约 3h后吸附达到平衡 ,不同吸附剂有不同的饱和吸附率 ;沸石、分子筛和蒙脱石是1 37Cs的强烈吸附剂 ,而青紫泥、小粉土和红壤则是廉价、实用的净化剂 ;矿物经活化处理后可提高对1 37Cs的吸附能力 ,其吸附率与粒径之间的关系呈幂回归形式 ,选择适当粒径的矿物可达到理想的吸附效果 ;由于拮抗作用 ,K离子可抑制吸附剂对水体中1 37Cs的吸附 ;1 37Cs在土壤中不易移动 ,0～ 5cm表土层中几乎集中了施入量的 99%以上。     

电解质阴离子和pH对可变电荷土壤硫酸盐吸附的影响

The effects of three electrolyte anions, ionic strength and pH on the adsorption of sulfate by two variable charge soils, with different surface charge properties were studied. Under the conditions of the same pH and ionic strength the effect of electrolyte anions on the adsorption of sulfate was in the order of Cl^- > NO₃^- > ClO₄^-, indicating the difference of the nature among these three anions. For Ferralsol in the same concentration of chloride and perchloride solutions, the two sulfate adsorption-pH curves could intersect at certain pH value. When pH was higher than the intersecting point, more sulfate was adsorbed in the perchloride solution, while when it was lower than the intersecting point, more sulfate was adsorbed in the chloride solution. In different concentrations of electrolyte solution, the curves of the amount of oxy-acid anion adsorbed, which changed with pH, could intersect at a certain pH, which is termed point of zero salt effect (PZSE) on adsorption. The nature of electrolyte anions influenced obviously the appearance of PZSE for sulfate adsorption. For ferralsol the curves of adsorption converged to about pH 7 in NaCl solution seemed to intersect in NaNO₃ solution and to have a typical PZSE for sulfate adsorption in NaClO₄ solution. For Acrisol the three curves of adsorption were nearly parallel in NaCl and NaNO₃ solutions and converged to pH 6.5 in NaClO₄ solution.     

不同条件下菲和萘在塿土上的吸附特征研究

以平衡吸附法研究了菲和萘在塿土上的吸附行为,考察了初始浓度、温度、pH、离子强度和CaCO3对塿土吸附菲和萘的影响,Henry方程、Freundlich方程和deBoer-Zwikker极化方程被用来拟和吸附等温线。结果表明,菲和萘在塿土上的吸附等温线为非线性,Freundlich方程最符合其吸附行为。菲和萘在塿土上的吸附量随温度升高而降低,其吸附是一个放热过程;吸附自由能小于零,表明吸附过程是自发的;熵变值也小于零,说明焓变是吸附过程的驱动力。随着pH增加,塿土对菲和萘的吸附量下降;而随着离子强度增加,塿土对菲和萘的吸附量增加。CaCO对菲和萘的吸附等温线也为非线性,其对塿土吸附菲和萘具有较大的贡献。     

Effect of sucrose on functional properties of soy globulins: adsorption and foam characteristics

In this contribution, we have analyzed the effect of sucrose on dynamic interfacial (dynamic surface pressure and surface dilatational properties) and foaming (foam capacity and foam stability) characteristics of soy globulins (7S and 11S). The protein (at 1 x 10(-3), 1 x 10(-2), 0.1, and 1 wt %) and sucrose (at 0, 0.25, 0.5, and 1.0 M) concentrations in aqueous solution and the pH (at 5 and 7), and ionic strength (at 0.05 and 0.5 M) were analyzed as variables. The temperature was maintained constant at 20 degrees C. We have observed the following. (i) The dynamics of adsorption (presence of a lag period, diffusion, and penetration at the air-water interface) of soy globulins depend on the peculiar molecular features of proteins (7S or 11S soy globulin) and the level of association/dissociation of these proteins by varying the pH and ionic strength, as well as the effect of sucrose in the aqueous phase on the unfolding of the protein. The rate of adsorption increases with the protein concentration in solution, at pH 7 compared to pH 5, at high ionic strength, and in the absence of sucrose. (ii) The surface dilatational properties reflect the fact that soy globulin adsorbed films exhibit viscoelastic behavior. The surface dilatational modulus increases at pH 7 compared to pH 5, but decreases with the addition of sucrose into the aqueous phase. (iii) The rate of adsorption and surface dilatational properties (surface dilatational modulus and phase angle) during adsorption at the air-water interface play an important role in the formation of foams generated from aqueous solutions of soy globulins. (iv) The increased interfacial adsorption (at high surface pressures) and the combined effects of interfacial adsorption and interfacial interactions between adsorbed soy globulin molecules (at high surface dilatational modulus) can explain the higher stability of the foam, with few exceptions.