Lability and sorption of heavy metals as related to chemical,physical, and mineralogical characteristics of highly weathered soils

Purpose  

Heavy metal lability, probably, is the most important isolated factor to cause toxicity in plants and organisms in soils. Sorption of heavy metals, in turn, affects directly the amount of their labile forms in soils. Therefore, to assess sorption and quantify labile forms of Cd, Cu, Ni, Pb, and Zn, adsorption and incubation studies were carried out.     

Organic and inorganic phosphate interactions with soil hydroxy-interlayered minerals

Background  

Even though extensive work has been done on P interactions with free Al- and Fe-hydroxide minerals, limited or no information exists on sorption/desorption processes of organic and inorganic phosphate forms with soil hydroxy-interlayered minerals.     

Mechanisms of phosphate retention by calcite: effects of magnesium and pH

Purpose

Sorption and precipitation of phosphate are important processes in controlling fate of phosphorus (P) in P-fertilized soils, especially those affected by magnesium (Mg) ions.

Materials and methods

The interaction between Mg(II) (0.42 and 8.33 mM) ions and phosphate (0.32 and 6.45 mM) at the calcite–water interface were investigated with various pH values from 6.0 to 12.0, using a combination of sorption envelopes, Fourier transform infrared spectroscopy, and X-ray diffraction.

Results and discussion

Amorphous calcium phosphate, dibasic calcium phosphate dihydrate, and hydroxyapatite are formed at high phosphate concentration (6.45 mM) and high pH (>8.0). The presence of low Mg(II) ion level (0.42 mM) had little effect on phosphate sorption. When Mg(II) ions increased to 8.33 mM, phosphate retention was inhibited in the weak acid condition since incorporation of Mg(II) ions kinetically hinders precipitation resulting in greater solubility of calcium phosphate while high pH favors Mg adsorption to provide more =Mg sites and OH functional groups on the surface of calcite, which enhanced the formation of Mg–P phases. The likely mechanism is attributed to the different surface terminations of calcite sorbed by phosphate at pH?<?8.0 and pH?>?8.0 in the presence of Mg(II) ions.

Conclusions

Our experimental results suggested that soil pH, initial concentration of phosphate, and the presence of Mg(II) ions and calcite play an important role to affect the fate of phosphate in P-fertilized soils.     

Effect of equilibration time on estimates of the maximum phosphorus sorption capacity of industrial by-products using the Langmuir model

Purpose

Using reactive industrial by-products (IBPs) to reduce phosphorus (P) losses associated with diffuse water pollution is a potentially cost-effective mitigation strategy. However, IBPs must be screened to assess their effectiveness and optimum application rates. This requires accurate estimates of parameters such as the maximum P sorption capacity. Traditionally, these parameters have been derived from the Langmuir model applied to data from batch sorption experiments following a 24-h equilibration period. In this paper, we examined (i) how equilibration time can influence estimates of the maximum P sorption capacity for IBPs and (ii) the relative P sorption characteristics of a range of IBPs available in the UK.

Materials and methods

Four IBPs containing different reactive components including ochre, aluminium (Al)-based water treatment residual (WTR), iron (Fe)-based WTR and Fe-lime (CaO)-based WTR were selected for this study. The maximum P sorption capacities of these IBPs were determined using a linearized Langmuir model applied to batch sorption data collected at different equilibration times of 24 h, 5 days and 10 days.

Results and discussion

The maximum P sorption capacity of ochre, Al-based WTR, Fe-based WTR and Fe-CaO-based WTR estimated from the linearized Langmuir model following a 24-h equilibration period was 10.1, 13.7, 2.4 and 9.3 mg P g^?1, respectively. However, extending the equilibration time from 24 h to 5 days increased the estimated maximum P sorption capacity for these IBPs by factors of 2.2, 2.1, 6.8 and 2.3, respectively. No significant increase was found in estimates of the maximum P sorption capacity when further extending the equilibration time to 10 days.

Conclusions

A minimum equilibration period of 5 days is recommended to avoid underestimating the maximum P sorption capacity of the IBPs examined in this paper. Each of the IBPs we evaluated was able to sorb P from solution, although with variable capacity (maximum sorption capacity after 5 days of equilibration ranged from 16.3–28.5 mg P g^?1). These findings emphasise the importance of accurate quantification of the P sorption capacity of IBPs before application.     

Effect of liming on phosphate sorption by acid soils

The sorption of phosphate (P) by four strongly acid Fijian soils from 0.01 M CaCl₂ decreased with increasing pH up to pH 5.5–6.0 and then increased again. The initial decrease in P sorption with increasing pH appears to result from an interaction between added P, negative charge, and the electrostatic potential in the plane of sorption. The results of a sorption study, involving KCl or CaCl₂ of varying concentrations as the background electrolyte and using Nadroloulou soil incubated with KOH or Ca(OH)₂, suggested that the increase in P sorption at pH values > 6.0 was caused by the formation of insoluble Ca-P compounds. For some soils this is consistent with the results of an isotopic-exchange study in which incubation with lime caused marked reductions in the amounts of exchangeable P at high pH.     

Changes in the sorption–desorption of fungicides over time in an amended sandy clay loam soil under laboratory conditions

Purpose

The aim of this work was to study the temporal changes in the sorption?Cdesorption of fungicides in a sandy clay loam soil amended with spent mushroom substrate (SMS) under controlled laboratory conditions and the influence that fungicides properties and soil characteristics have on these processes. Soil amendment with SMS is becoming a widespread management practice since it can effectively solve the problems of uncontrolled SMS accumulation and disposal and improve soil quality. However, when simultaneously applied with pesticides, SMS can significantly modify the environmental behaviour of these compounds.

Materials and methods

Sorption?Cdesorption isotherms of metalaxyl, penconazole, pyrimethanil and iprovalicarb for unamended and amended vineyard soils from La Rioja (Spain) were obtained. Composted SMS (C-SMS) and fresh SMS (F-SMS) from cultivation of different mushrooms were used as amendments at 2?% and 10?% rates. Soil parameters (organic carbon (OC), dissolved organic carbon (DOC), humic acid (HA) and fulvic acid (FA)) and sorption (Kf, nf, Kd, Koc) and desorption (Kfd, nfd, H) parameters of fungicides were determined over 0, 6 and 12?months of soil incubation with SMS under controlled conditions.

Results and discussion

Addition of amendments to soil increased soil sorption capacity of fungicides. Kd values increased with the hydrophobic character of fungicides (metalaxyl?<?iprovalicarb?<?pyrimethanil?<?penconazole) at both amendment rates. The lower content of DOC and the higher degree of OC humification enhanced sorption of all fungicides by the soil?+?C-SMS with regard to the soil?+?F-SMS. In general, sorption of fungicides decreased after 6 and 12?months of soil?+?SMS incubation, although the humification degree of the remaining OC expressed by HA/FA increased. This might indicate that the OC content was more important for fungicide sorption than the changes in its nature with the incubation time. SMS addition favoured desorption of metalaxyl and iprovalicarb, in general, whereas irreversible sorption of penconazole and pyrimethanil increased. However, the opposite trends were observed when the soil?+ SMS incubation time increased.

Conclusions

The results show an increase in sorption of all fungicides by amending soil with composted or fresh SMS. However, desorption of fungicides increases or decreases depending on the properties of fungicides and soil?+ SMS. Changes in both processes with the incubation time are more related to the OC content of the amended soil than to the evolution of its nature. These outcomes are of interest for extending SMS application to soil with minimal or no environmental risk when used simultaneously with fungicides.     

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.     

EFFECTS OF SOLUTION: SOIL RATIO ON PHOSPHATE SORPTION BY SOILS

Isotherms for the sorption of inorganic phosphate (P) by three contrasting soils during 40 h showed a dependence on solution: soil ratio. Above a final solution P concentration of 0.5 μg ml^?1, more P was sorbed at a solution: soil ratio of 5:1 than at 40:1 for a given level of P in solution. With time up to 146 h, the effect of solution: soil ratio on P sorption was kinetically controlled. Equilibrium solution P concentrations, estimated by extrapolation of the linear relationships between solution P concentration and the reciprocal of time to I/t= o (i.e. t=∞)appeared to be coincident for each solution:soil ratio at high and the low levels of added P. Consequently, sorption isotherms at equilibrium would be coincident, irrespective of the solution soil ratio used. The kinetic control of solution: soil ratio on P sorption is interpreted in terms of the number of P sorbing sites and initial solution P concentration on the rate of P sorption by soils.     

Kinetics and binding capacity of six soils for structurally defined hydrolyzable and condensed tannins and related phenols

Purpose  

We investigated tannin–soil interactions by assessing the kinetics of sorption and sorption capacities, and their relationship to the chemical properties of six polyphenolic compounds and the textures of six soils. We developed a new extraction procedure for recovering tannins from soil samples by successive extraction with solvents of decreasing polarity.     

Differences in sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid on artificial soils as a function of soil pre-aging

Purpose

The sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) to three different artificial soil mixtures was investigated. Artificial soils serve as model systems for improving understanding of sorption phenomena.

Materials and methods

The soils consisted of quartz, ferrihydrite, illite, montmorillonite, and charcoal. In a previous study, several selected mixtures had been inoculated with organic matter, and microbial aging (incubation) had been performed for different periods of time (3, 12, and 18?months) before conducting the sorption experiments. The effect of this pre-incubation time on the sorption behavior was determined. Interaction of MCPA with soil surfaces was monitored by aqueous phase sorption experiments, using high-performance liquid chromatography/ultraviolet and in selected cases Fourier-transformed infrared spectroscopy.

Results and discussion

The sorption behavior showed large differences between differently aged soils; Freundlich and linear sorption model fits (with sorption constants K _f , 1/n exponents, and K _d values, respectively) were given for pH?=?3 and the unbuffered pH of ??7. The largest extent of sorption from diluted solutions was found on the surfaces with a pre-incubation time of 3?months. Sorption increased at acidic pH values.

Conclusions

Regarding the influence of aging of artificial soils, the following conclusions were drawn: young artificial soils exhibit stronger sorption at lower concentrations, with a larger K _f value than aged soils. A correlation with organic carbon content was not confirmed. Thus, the sorption characteristics of the soils are more influenced by the aging of the organic carbon than by the organic carbon content itself.     

Sorption of the herbicide terbuthylazine in two New Zealand forest soils amended with biosolids and biochars

Background, aim, and scope  

Terbuthylazine is one of the most commonly used herbicides for vegetation management in forest plantations in New Zealand. Knowledge about the sorption of terbuthylazine on forest soils, especially the influence of coexisting organic amendments, remains obscure. In this study, we evaluated the effects of biosolids and biochars on the sorption of terbuthylazine to forest soils.     

Effect of aggregation on the adsorption of phosphorus onto air-dried sediment in contrasting shear flow conditions

Purpose

Fine sediments are usually collected in situ and air-dried for adsorption experiments, which may lead to particle aggregation and thus have a significant effect on phosphorus (P) adsorption under dynamic conditions. The main purpose of this study was to investigate the changes of aggregates due to drying with shear stress and the effects on the adsorption of P onto air-dried sediments under different shear rates after re-wetting.

Materials and methods

Sediment samples were collected from an alluvial river. Fine wet sediments (<31 μm) were wet-sieved and air-dried, and some air-dried sediments were further sonicated and served as the control. The grain size distribution of the three sediment samples (wet, dried, and sonicated) was measured to evaluate the particle aggregation level. The P sorption capacity of wet and dried sediments was determined by batch equilibrium experiments. The change of aggregate size with shear stress was investigated for dried and sonicated sediments. Sorption equilibrium experiments were performed to investigate the effect of shear stress on the P sorption with and without change of particle aggregation level, respectively.

Results and discussion

Fine particles agglomerated into larger aggregates during the drying process, resulting in a significant increase in the aggregate size. The sorption capacity was lower in aggregated sediment than in original wet sediment. Aggregate size in dried sediment decreased with the increase of shear rate, leading to an increase in the surface area and available adsorption sites, whereas the particle size of sonicated sediment was hardly affected. Accordingly, the P sorption amount of dried sediment increased with increasing shear rate, whereas that of sonicated sediment showed no significant change with shear rate after all sediments were suspended. There was a significant curvilinear correlation between aggregate size and P sorption amount for dried sediments, thus indicating that the P sorption amount increased significantly with decreasing aggregate size.

Conclusions

Sediment aggregation is an important factor affecting P adsorption besides the amount of suspended sediments and the exchange between suspended and bed sediments under dynamic conditions. The P equilibrium adsorption amount increases with shear stress for air-dried sediment. The effect of particle aggregation on the amount of P sorbed onto sediments should not be ignored, and thus, more attention should be paid to the pretreatment of sediment samples in the sorption experiments under dynamic conditions.

     

Enhanced sorption of polycyclic aromatic hydrocarbons by soil amended with biochar

Purpose  

Polycyclic aromatic hydrocarbon (PAHs) are ubiquitous pollutants in agricultural soils in China. Biochar is the charred product of biomass pyrolysis, which is widely applied to soils to sequestrate atmospheric carbon dioxide and guarantees a long-term benefit for soil fertility. Knowledge about the impacts of various biochars on soil sorption affinity remains obscure. In this study, we evaluated the effects of various biochars on PAHs sorption to biochar-amended agricultural soil.     

Effect of soil components on the surfactant-enhanced soil sorption of PAHs

Purpose  

The use of cationic surfactants was proposed to enhance the soil retention of hydrophobic organic contaminants (HOCs). However, due to the complexity of soil composition, the effect of cationic surfactants on the soil sorption of HOCs was limited to a qualitative understanding. To gain further insight into the mechanism of the surfactant and predict its efficiency, a comparative study on the HOCs sorption capacities of the surfactants sorbed on pure typical soil components was investigated.     

Dynamics of arsenic-containing compounds sorption on sediments

Background  River and lake sediments constitute complex and difficult analytical samples. On the other hand, sediments play a fundamental role in the distribution of toxic compounds in aquatic systems and in the evaluation of the current state and the course of changes taking place in the environment. Among elements present in the environment in trace concentrations, but having well-elaborated toxic properties, one of most dangerous is arsenic. The element occurs in the environment in several chemical forms, predominant are inorganic forms of As(V) and As(III), and methylated forms such as monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA). Objectives  Reported herein are experiments, which were undertaken with the aim of examining the dynamics of arsenic sorption in sediments and its dependence on speciation of the element and the pH in the environment. Simultaneously, influence of organic matter content and chemical composition of the sediments on As sorption, were investigated. Methods  Sediment samples (upper 10 cm layer) were collected from three sites located in the vicinity of Cracow:

TiO<Subscript>2</Subscript> photocatalytic degradation of 4-chlorobiphenyl as affected by solvents and surfactants

Purpose  

TiO₂ photocatalytic degradation of 4-chlorobiphenyl (PCB3) in aqueous solution under UV irradiation was investigated as affected by different environmental factors, including initial PCB3 concentration, TiO₂ content, UV intensity, H₂O₂ concentration, cosolvents, and surfactants.     

Effects of fresh and degraded dissolved organic matter derived from maize straw on copper sorption onto farmland loess

Purpose

The nature of dissolved organic matter (DOM) strongly influences heavy metal sorption onto soil. However, the constituents and structures of DOM change continuously as DOM is subjected to microbial decomposition and photodegradation at natural field scales. Thus, this study was designed to explore the effects of chemical changes of DOM on heavy metal sorption onto farmland soil in natural degradation.

Materials and methods

Fresh DOM (FDOM) and degraded DOM (DDOM) both were extracted from the straw of maize which was extensively planted in Loess Plateau, China. The characteristics of DOM were determined by Fourier transform infrared spectroscopy (FTIR), elemental analysis, excitation-emission matrix (EEM) fluorescence spectra, UV-visible spectra (UV-vis), nuclear magnetic resonance (NMR), and molecular weight analysis. Farmland loess soil in Loess Plateau and heavy metal Cu(II) which can easily form a complex with DOM in soil were employed to investigate the effects of DOM dynamic changes on Cu(II) sorption onto loess through batch tests.

Results and discussion

Compared with FDOM, DDOM changed significantly in composition including oxygen content, functional group species, aromatic properties, and molecular weight distribution. Oxygen content, aromaticity, and low-molecular-weight fraction (<3 kDa) decreased while aromatic substitution and high-molecular-weight fraction (>10 kDa) increased for DDOM. For these changes, the effects of FDOM and DDOM on heavy metal Cu(II) sorption onto loess were significantly different due to DOM-Cu(II) binding ability varied with FDOM degradation. FDOM promoted Cu(II) sorption onto loess at Cu(II) concentration below 400 mg l^?1 while inhibited above 400 mg l^?1, but DDOM always showed inhibition effects on Cu(II) sorption onto loess. Moreover, both the promotion and inhibition effects depended mainly on the initial concentrations and pH values of FDOM and DDOM.

Conclusions

The results of the present study demonstrate that chemical characteristics of FDOM and DDOM are greatly diverse in components, functional group species, molecular weight distribution, etc. although they are from the same source. The apparent differences can explain their distinct effects on copper sorption onto loess soil. Hence, future researches are supposed to focus on the dynamic changes of DOMs when evaluating their influence on heavy metals environmental behaviors under actual conditions.

     

Testing a mechanistic model. II. The effects of time and temperature on the reaction of zinc with a soil

Samples of a soil were mixed with zinc nitrate solutions and incubated from 1 to 30 days at temperatures from 4 to 60°C. The solution concentration of zinc, which would not have changed on brief mixing with the soil at 25°C, was measured. Background electrolytes for this measurement of null-point concentration were both calcium and sodium nitrate. The effect of the temperature at which null-point concentration was measured was also investigated. After incubation with zinc nitrate, desorption of zinc, and sorption of further zinc, were measured. Null-point concentration of zinc decreased with increasing period of incubation, with the rate of decrease greatest at high temperatures of incubation. The effects of both temperature and time were closely described by a model which postulated an initial rapid adsorption of ZnOH⁺ ions onto heterogenous charged surfaces, followed by a diffusive penetration. Increasing the temperature of incubation increased the rate of diffusive penetration and led to low solution concentrations. In contrast, increasing the temperature at which null-points were measured increased the concentration of ZnOH⁺ ions. This was shown to be consistent with a change in position of the equilibrium of the initial, rapid, adsorption reaction. Curves for desorption of zinc were continuous with curves for sorption of further zinc, but neither desorption nor further sorption coincided with the position of the curves relating retention of previously added zinc to concentration. This result was consistent with the model and occurred because desorption must reverse diffusive penetration. However, the model under-predicted the magnitude of both desorption and sorption of further zinc. Desorption in calcium solutions was greater than in sodium solutions, even when the solution concentration of zinc approached zero. This was consistent with exchange diffusion of calcium ions for some of the penetrated zinc.     

Dissipation and sorption processes of polycyclic aromatic hydrocarbons (PAHs) to organic matter in soils amended by exogenous rich-carbon material

Purpose

The aim of the research was to assess the effect of biochar addition on aging, degradation, and sorption processes of polycyclic aromatic hydrocarbons (PAHs) to soil organic matter. The study was carried out as a sorption experiment in strictly controlled water and air conditions, which allowed for the accurate observation and prediction of PAH behavior in soils.

Materials and methods

Four soils were fortified with a PAH mixture (Fluorene-Flu, Anthracene-Ant, Phenanthrene-Phe, Pyrene-Pyr, Chrysene-Chry) at 20 mg kg^?1 of single-compound concentration level. The experiment was carried out in two trials: soils?+?5PAHs amended with biochar and soil?+?5PAHs without biochar addition with incubation times of 0, 1, 3, 6, and 9 months. After each interval time, the extractable (E-SOM) and stable organic matter (S-SOM) were measured as well as PAHs determined in two forms: total concentration (PAH-tot) and residual concentration (PAH-rest) after E-SOM extraction. The PAH loss and half-life times were estimated according to pseudo first-order kinetics equation.

Results and discussion

The amounts of PAH-tot in the soils without biochar decreased by an average of 92%, while in soil with biochar, this was 41% after 9 months of aging. The amount of PAHs-rest bounded with S-SOM after 9 months of incubation varied from 0.9 to 3.5% and 0.2 to 1.3% of the initial PAH concentration, respectively, for soils non-induced and induced by biochar. In soils without biochar, Flu, Ant, Phe, and Pyr exhibited similar T_1/2 (43–59 days), but Chry was characterized by a much higher and broader T_1/2 than other hydrocarbons (67–280 days). Biochar addition to the soils significantly influenced the half-life changes for all PAHs. The highest changes were noted for Phe (14-fold increase), and the lowest was for Flu (7-fold increase).

Conclusions

The addition of exogenous-rich carbon material such as biochar to the soil significantly changes the behavior and sorption potential of PAHs in the soil. Soils enriched with biochar are characterized by a higher persistence of PAHs, longer aging time, and lower affinity for sorption by native organic matter structures. Soils freshly polluted by PAH are mainly sorbed by E-SOM, which significantly increases their accessibility and reduces formation of bound-residues in the soil.

     

Sorption and persistence of wastewater-borne psychoactive and antilipidemic drugs in soils

Purpose  

Although the ubiquity of pharmaceuticals in treated wastewater has now been well documented, their fate and risk during beneficial wastewater reuse are far less understood. Soil sorption and degradation are important processes affecting the leaching potential of trace contaminants in irrigated soil. To this end, we examined the sorption and attenuation of six psychoactive and antilipidemic drugs, i.e., carbamazepine, diazepam, Dilantin, meprobamate, primidone, and gemfibrozil, in a loam (LVL) and a loamy sand representative of golf course soils in the southwestern United States.