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1.
Abstract

To evaluate contributions of organic matter, oxides, and clay fraction to copper (Cu) adsorption in six characterized soils, adsorption isotherms and distribution coefficients were obtained by a batch experimental method. Copper adsorption isotherms from untreated soil, organic matter removed from samples, and organic‐matter‐ and oxide‐removed samples were compared with curve patterns and correlated to Langmuir and Freundlich models. Copper sorption data on untreated soils described L or H‐curves, whereas in soils deprived of any component, their curves were S‐type. Distribution coefficients allowed knowing Cu adsorption capacity of untreated soil and of organic matter, oxides, and clay fraction. Soil organic matter is the main component that affects Cu adsorption as long as soil pH is near neutrality. At acid pH, oxides are the main component that affects Cu adsorption, although to a much smaller extent than organic matter near neutral conditions. Soil pH is the main soil factor that determines Cu adsorption.  相似文献   

2.
The present study investigated the impact of long‐term soil management on the metal retention capacity of soil. We examined the sorption behaviour of Cu, Cd and Zn in soils and in the various particle‐size fractions of these soils, which had been amended with farmyard manure, mineral fertilizers or were fallow for 38 years in a long‐term field experiment. The soils investigated contained different amounts and origins of organic matter and differed in soil pH, but the mineral phase showed less response to the different soil managements. Batch adsorption and desorption experiments as well as a sequential fractionation schema, which defines seven geochemical fractions, were used to investigate the retention properties of soil. Sequential extraction was conducted with original as well as with metal‐spiked soils. Results showed that amounts of Cu, Cd and Zn retained differed by a factor of more than 3 among the treatments in the long‐term field experiment, when a massive concentration of metal was added to soil. An increased sorption on smaller particle size fractions occurred (clay ≫ silt > fine sand ≥ coarse sand) due to the larger surface area as well as the greater carbon content in the smaller fractions. Soil sorption behaviour in another long‐term field experiment was estimated based on the present particle‐sorption data. Differences in the sorption behaviour were related to differences in soil mineralogy and amounts of Fe‐ and Mn‐oxides. Fractionation of the original and the metal‐spiked soil underlined the contribution of organic matter to sorption capacity (sequence: Cu ≫ Cd > Zn). Different organic matter contents and a different soil pH considerably changed the amounts of metals in the defined geochemical fractions. Freshly added Cu, Cd and Zn ions were found mainly in more mobile fractions. In contrast, metals in non‐spiked soils appeared in less‐mobile fractions reflecting their long‐term sorption behaviour.  相似文献   

3.
Solution cadmium (Cd) concentrations and sorption and desorption of native and added Cd were studied in a range of New Zealand soils. The concentration of Cd in solution and the concentrations and patterns of native soil Cd desorbed and added Cd sorbed and desorbed varied greatly between the 29 soils studied. Correlation analysis revealed that pH was the most dominant soil variable affecting solution Cd concentration and sorption and desorption of native and added Cd in these soils. However, organic matter, cation exchange capacity (CEC) and total soil Cd were also found to be important. Multiple regression analysis showed that the log concentration of Cd in solution was strongly related to soil pH, organic matter and total Cd, which in combination explained 76% of the variation between soils. When data from the present study were combined into a single multiple regression with soil data from a previously published study, the equation generated could explain 81% of the variation in log Cd solution concentration. This reinforces the importance of pH, organic matter and total Cd in controlling solution Cd concentrations. Simple linear regression analysis could at best explain 53% of the total variation in Cd sorption or desorption for the soils studied. Multiple regression analysis showed that native Cd desorption was related to pH, organic matter and total Cd, which in combination explained 85% of the variation between soils. For sorption of Cd (from 2 μg Cd g–1 soil added), pH and organic matter in combination explained 75% of the variation between soils. However, for added Cd desorption (%), pH and CEC explained 77%. It is clear that the combined effects of a range of soil properties control the concentration of Cd in solution, and of sorption and desorption of Cd in soils. The fraction of potentially desorbable added Cd in soils could also be predicted from a soil’s Kd value. This could have value for assessing both the mobility of Cd in soil and its likely availability to plants.  相似文献   

4.
Abstract

The adsorption of selenium (Se) in the selenate form and its desorption by phosphate in four soils with different physiochemical properties were studied in the laboratory. To determine adsorption isotherms for selenate 25 mL of solutions containing 1 to 100 ppm of Se were added to 2.5 g of soil. Desorption isotherms were determined by resuspending the samples in phosphate solution. The selenate sorption process was adequately described by the Freundlich equation. In pine forest and woodland soils, characterized by the highest organic matter content and cation exchange capacity (CEC) values, the isotherms were classified as L type, since the amount of Se sorbed appeared to move towards saturation. The organic matter content played the most important part in the adsorption of Se, while pH appeared to have a small effect on the ability of the soil to adsorb Se. The high CaCO3 content of the pine forest soil may have contributed in increasing the Se adsorption notwithstanding the high pH value. The cultivated and arable soils showed a reduced sorption capacity. The sorption could be described by an S type curve. At low concentrations of Se the affinity of the solid phase was less than that of the liquid phase. By increasing the concentration of Se in solution, the affinity of the solid phase increased and the sorption was favored. Selenate desorption by water was negligible, whereas the amount of Se desorbed by phosphate varied among the different soils. The desorption experiments indicated that a significant portion of the sorbed Se was irreversibly retained. This suggests the existence of linkages which allow the release of Se in the soil solution only after physico‐chemical variation such as exchange with phosphate ions.  相似文献   

5.
Abstract

Copper (Cu) deficiency exists in different rice growing areas of Malaysia. A study on Cu adsorption was carried out in three Malaysian rice soils (Idris, Tebengau, and Kangar series) using six levels of Cu (0, 100, 200, 300, 400, and 500 ug g‐1). The data on Cu adsorption were fitted into Langmuir, Freundlich, and Temkin equations. Adsorption data were also correlated with pH, cation exchange capacity, and organic matter content of the soils. The effect of Cu addition on redox potential (Eh) of the soils was also measured. The Eh values were correlated with equilibrium solution Cu concentrations. Copper adsorption increased gradually with increasing level of added Cu in all the soils. The rate of increase was the highest in Kangar series followed by Tebengau and Idris, respectively. Correlation between Cu adsorption and pH was significant (r=0.772) whereas correlation of adsorption with either organic matter content or cation exchange capacity was nonsignificant. Copper adsorption in two soils (Idris and Tebengau) fitted Langmuir, Freundlich, and Temkin equations whereas Cu adsorption in the Kangar soil fitted Freundlich and Temkin equations. Redox potential (Eh) of the soils increased gradually with increasing level of added Cu. The rate of increase was the highest in Idris followed by Kangar and Tebengau soils, respectively. The relationship between equilibrium solution Cu concentration and redox potential was significant. The results of this study indicated that copper adsorption is mainly dependent on soil pH. In soils with higher adsorption capacity, more Cu fertilizer may be needed to get immediate crop response.  相似文献   

6.
The objective of this study was to examine the effect of soil pH on zinc (Zn) sorption and desorption for four surface soils from the Canterbury Plains region of New Zealand. Zinc sorption by the soils, adjusted to different pH values, was measured from various initial solution Zn concentrations in the presence of 0.01 M calcium nitrate [Ca(NO3)2]. Zinc desorption isotherms were derived from the cumulative Zn desorbed (µg g?1 soil) after each of 10 desorption periods by sequentially suspending the same soil samples in fresh Zn‐free 0.01 M Ca(NO3)2. Zinc sorption and desorption varied widely with soil pH. Desorption of both native and added Zn decreased continuously with rising pH and became very low at pH values greater than 6.5. The proportion of sorbed Zn that could be desorbed back into solution decreased substantially as pH increased to more than 5.5. However, there were differences between soils regarding the extent of the hysteresis effect.  相似文献   

7.
土壤对铜离子的专性吸附及其特征的研究   总被引：24，自引：4，他引：24  
武玫玲 《土壤学报》1989,26(1):31-41
供试土壤专性吸附铜的等温线均符合Langmuir方程。红壤吸附量最低,砖红腹与黄泥土最大吸附量相近,但在铜浓度低时砖红壤吸铜量远低于黄泥土,而在高浓度则反之。土壤专性吸附铜是在溶液中Na+浓度比Cu2+高8.3—100倍条件下,Na+离子仍不足以与之竞争的那些专性吸附点所吸持的铜。按其解吸条件区分为松结合铜(可为N NH4Cl解吸)和紧结合铜(仅能为0.1 N HCl解吸)两种。紧结合铜受平衡溶液铜浓度影响很小,所占据的吸附点对Cu2+有较强亲和力。松结合铜则随平衡铜溶液浓度增大而增加,符合Langmuir方程。对于砖红壤和黄泥土,在铜浓度低时紧结合铜>松结合铜;浓度高时则反之。红壤专性吸附铜始终以松结合铜为主。三种土壤比较,紧结合铜是砖红壤>黄泥土>红壤;松结合铜则是黄泥土>砖红壤>红壤。造成这些差别的原因可能与土壤性质、氧化物、有机质和粘土矿物组成等不同有关。用平衡法研究三种土壤专性吸附铜在不同浓度NH4Cl和HCl溶液中的解吸表明,可进一步区分为三或四种不同的结合状况。红壤对铜吸附容量最小,且最易解吸。  相似文献   

8.
Abstract

The importance of various soil components on copper (Cu) retention by Spodosois was investigated. Copper sorption and extraction were conducted on samples from the B horizon from six Danish Spodosois. The investigation was conducted on untreated samples, on hydrogen peroxide‐treated samples (to remove organic matter), on oxalate‐treated samples [to remove amorphous to poorly crystalline aluminum (Al) and iron (Fe) oxides], on hydroxylamine‐treated samples [to remove manganese (Mn) oxides]. Subfractions treated with hydrogen peroxide (H2O2) were further treated with oxalate and citrate‐bicarbonate‐dithionite (CBD). Sorption of Cu from an initial 10‐6 M solution after 48 hours was determined in the pH range 3 to 7 using 0.1M sodium nitrate (NaNO3) as the background electrolyte. The pH‐dependent sorption curve (sorption edge) was shifted to a higher pH with decreasing Al oxide content in the soils, and for the treated sample after removal of organic matter and Al and Fe oxides. A negligible effect was seen after removal of the Mn oxides because of their low abundance. Extraction of sorbed Cu at pH 4 to 6 with 0.1M nitric acid (HNO3) for 24 hours confirmed the sorption results, in inasmuch as removal of the Al (and Fe) oxides increased Cu extractability. Therefore, it was concluded that in the soils investigated, Cu retention is mainly determined by the oxalate‐extractable Al fraction with a minor contribution due to crystalline Fe oxides.  相似文献   

9.
This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients KF increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO3)2 < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants KF and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.  相似文献   

10.
The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N2 method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.  相似文献   

11.
The study about the adsorption of phosphate on four variable charge soils and some minerals revealed that two stage adsorption appeared in the adsorption isotherms of phosphate on 4 soils and there was a maximum adsorption on Al-oxide-typed surfaces between pH 3.5 to pH 5.5 as suspension pH changed from 2 to 9, but the adsorption amount of phosphate decreased continually as pH rose on Fe-oxide typed surfaces. The adsorption amount of phosphate and the maximum phosphate adsorption pH decreased in the order of yellow-red soil > lateritic red soil > red soil > paddy soil, which was coincided with the content order of amorphous Al oxide. The removement of organic matter and Fe oxide made the maximum phosphate adsorption pH rise from 4.0 to 5.0 and 4.5, respectively. The desorption curves with pH of four soils showed that phosphate desorbed least at pH 5. Generally the desorption was contrary to the adsorption with pH changing.  相似文献   

12.
Adsorption of Cu and the cationic herbicide chlordimeformwas carried out on two acidic soils (S-48 and LM).Chlordimeform adsorption occurred by cationic exchange andwas higher on LM soil due to its higher CEC, partlyassociated to the presence of vermiculite. Cu adsorptionwas also higher on LM soil and was related to its higheriron and manganese oxides content. The presence of theherbicide in solution always decreased Cu adsorption on S-48 soil, but on LM soil the amount of Cu adsorbed onlydecreased at the highest concentrations used. This togetherwith the lower amounts of Cu desorbed from LM soil afterfive successive desorptions in comparison to S-48 soil,indicates that Cu was being mostly adsorbed on oxides whichexhibit a very high affinity for the heavy metal. Themaximal amount of Cu desorbed on both soils only reached upto 13% of the amount adsorbed. Chlordimeform adsorption decreased in the presence of Cu as aresult of its competition for the adsorption sites on bothsoils. Cu competition on LM soil was not so strong as on S-48 soil due to the higher adsorption of the heavy metal onoxides, for which the herbicide’s affinity is not so high. Thelower the amounts of chlordimeform adsorbed on both soilsthe higher its desorption percentage. This was attributedto steric impediment of chlordimeform molecule itself forthe desorption from lamellar silicates.  相似文献   

13.
干旱区绿洲灌漠土对铜的吸附解吸特性研究   总被引：2，自引：1，他引：1  
土壤对重金属的吸附解吸是影响土壤系统中重金属的移动性和归宿的主要过程.本文使用序批实验方法、单步提取方法、连续提取方法等研究了干旱区绿洲灌漠土Cu的吸附解吸特性.结果表明,灌漠土对Cu的吸附等温线可很好地用Freundlich等温方程拟合,灌漠土的Cu吸附可能受土壤理化综合因素影响,而不仅是某个土壤理化指标所控制;二次...  相似文献   

14.
Copper sorption was measured in 14 agricultural soils from England and Wales with a wide range of properties. Sorption from 0.01 M CaCl2 was described by the Freundlich adsorption isotherm when Cu in solution was initially at 200 HM and greater, but at lower initial concentrations (i. e. 100 fiM and less) there was a steep rise in the gradients of the isotherms. At initial concentrations of 100 JIM and less, sorption was linearly correlated to the concentration of Cu remaining in solution; the gradients of these relationships varied considerably amongst the soils and were highly correlated to soil pH. There was no correlation between either the gradients or the extrapolated values of final solution concentration at which there was no sorption of added Cu by the soils (an ‘equilibrium’ concentration), and other determined soil properties. The effect of pH adjustment on sorption varied between the 5 soils examined although, in general, there was increasing sorption with increasing pH. Extrapolated values for ‘equilibrium’ concentrations for an individual soil were higher at pH 6.0 or greater, than at pH 5.5. A large proportion of the Cu in the final solutions was apparently complexed but this varied between soils and was dependent on both pH and total concentration. There was little effect of varying pH of the final solution on these proportions in most soils. Neither extractable Cu in the soils, nor the sorption characteristics were related to availability as measured by uptake by perennial ryegrass.  相似文献   

15.
Low‐molecular‐weight (LMW) organic acids exist widely in soils, especially in the rhizosphere, and the adsorption of these acids may affect their reactions in soils. The adsorption behaviour of phthalic acid and salicylic acid by two variable charge soils (a Rhodic Ferralsol and a Haplic Acrisol) was investigated. Both soils exhibited great adsorption capacity for these organic acids, with a greater affinity for phthalic acid. The Rhodic Ferralsol adsorbed more organic acids of both kinds than the Haplic Acrisol, which was consistent with the content of iron and aluminum oxides in the two soils. The iron oxides in these soils played a significant role in adsorption of the organic acids, whilst the soil aluminosilicate minerals, such as kaolinite, showed a small adsorption capacity. The presence of phosphate and sulphate caused a decrease in the adsorption of both organic acids because of their competition with them for sorption sites. The phosphate showed a bigger inhibition on the adsorption than sulphate as a result of a greater amount of phosphate adsorbed by the soils. The adsorption of both organic acids was affected by pH only slightly at pH < 4.5. However, the adsorption decreased with the increase in pH at pH > 4.5. A similar trend was observed for the phosphate system, but the opposite was seen for the sulphate system. This suggests that the inhibition of sulphate on the adsorption of the organic acids decreased with the increase in pH, because the adsorption of sulphate decreased strongly with increasing pH.  相似文献   

16.
Copper adsorption and desorption under acid conditions by soil clay fractions separated from Vertisol, Planosol and Gleyic Acrisol has been studied in 0.01 M Ca(NO3)2. A Freundlich equation was appropriate to describe Cu adsorption. Within the range of 150 to 2600 mg of copper per kg of soil clay fraction the proportions of Cu not displaced during 5 successive 48-hour desorptions with 0.01 M Ca(NO3)2 decreased with increasing adsorption density and at the lower pHs. The proportions ranged from as high as 0.98 in th case of the Vertisol clay (pH 5.3) to as low as 0.12 (88% desorption) in the Planosol clay (pH 4.5). Measurement of separation factors (ga Cu/Ca) showed that the preference of the clay surface for Cu over Ca decreased in the order: Gleyic Acrisol > Planosol > Vertisol. A considerable amount of sorbed copper could be solubilized by decreasing pH values to 4 when in the Planosol clay 39% was desorbed and 45% was desorbed in the Gleyic Acrisol clay.  相似文献   

17.
Cadmium (Cd) sorption and desorption characteristics by Alfisols from different land uses were examined, and the relationships between soil and sorption/desorption characteristics were investigated. Adsorption studies were done using Cd concentrations (0–100 mg Cd kg?1) in 0.01 M CaCl2. The Cd sorbed by the soils was then subjected to two desorption runs. The soils' adsorption conformed to Freundlich and Langmuir equations. The amount of Cd sorbed by the soils varied. Two desorption runs detached more than 95% of sorbed Cd, but the first accounted for more than 80% of the total. Desorption of Cd in degraded soils was more than in soils from other land uses. The amount of Cd desorbed correlated with amount applied (r = 0.90??), solution concentration (r = 0.83??), and amount sorbed (r = 0.70??). A positive relationship exists between the adsorption maxima of the soils and soil organic matter (r = 0.13, p = 0.87). The relationship between amount of Cd desorbed and sorbed is quadratic for all the soil.  相似文献   

18.

Purpose

Sorption of heavy metals on soil components plays an important role in reducing their mobility and bioavailability. Organic matter is an important sorbent of heavy metals in soil. Crop residues which are important sources of soil organic matter will undergo decomposition after addition to the soil. However, few studies reported the effect of organic matter decomposition on heavy metal sorption. This study aimed to investigate the effect of straw decomposition on the sorption of Cu.

Materials and methods

Rice straw was decomposed in aerobic conditions for 1, 3, 6, and 12 months, respectively. Solid organic matter in decomposed rice straw was collected and marked OM-1, OM-3, OM-6, and OM-12, respectively. Sorption isotherms and kinetics of Cu on solid organic matter were studied by batch experiments. The sorption of Cu was calculated by the difference between the amount of Cu added initially and that remained in the supernatant. Sorption thermodynamics of Cu were studied by isothermal titration calorimetry technique. Potential mechanisms of Cu sorption were analyzed by combining the information from sorption thermodynamics, desorption experiments, and Fourier transform infrared spectroscopy observations. All sorption experiments were carried out at pH 5.0.

Results and discussion

The maximum sorption of Cu was 165.8, 170.5, 186.6, and 226.9 mmol kg?1, and the rate constant of Cu sorption was 0.80, 0.58, 0.50, and 0.32 kg mmol?1 h?1 on OM-1, OM-3, OM-6, and OM-12, respectively, indicating that the maximum sorption of Cu increased while sorption rate of Cu decreased with increasing the duration of straw decomposition from 1 to 12 months. The negative values of Gibbs free energy change and positive values of enthalpy change and entropy change revealed that Cu sorption was spontaneous, endothermic in nature, and the randomness was increased during sorption. Carboxyl and hydroxyl in solid organic matter were involved in Cu sorption. The percentage of Cu desorbed by NH4Ac from OM-1, OM-3, OM-6, and OM-12 was 45.0, 43.5, 42.8, and 37.8 %, respectively.

Conclusions

In the current study, the decomposition of straw promoted the sorption capacity but reduced the sorption rate of Cu on solid organic matter. Copper sorption was an endothermic and spontaneous process. The formation of inner-sphere complexes was the main mechanism of Cu sorption, and its role in Cu sorption tended to increase with increasing the duration of straw decomposition. The information will facilitate the understanding of the contamination and remediation of heavy metal in cropland.
  相似文献   

19.
土层性质对铜和铅在土壤中保持和迁移的影响   总被引：1，自引：0，他引：1  
The mobility and bioavailability of heavy metals in soils is largely governed by sorption and desorption phenomena.Cu2+ and Pb2+ are among the most potentially toxic heavy metals and they are present,often concomitantly,in many polluting spills and in agrochemicals.The objective was to assess and compare the competitive sorption and desorption capacities and sorption hysteresis of Cu2+ and Pb2+,as well as their migration through the profiles of four natural soils:a Humic Umbrisol,an Umbric Cambisol,an Endoleptic Luvisol and a Humic Cambisol.In all horizons Pb2+ was invariably sorbed and retained to a greater extent than Cu2+.The sorption and retention of Cu2+ were most in?uenced by pH,e?ective cation exchange capacity(CECe) and Mn oxide content.On the other hand,the fixation capacity of Pb2+ was most in?uenced by pH,CECe,and Mn oxide and organic matter contents.pH and CECe were the individual soil properties most markedly in?uencing Cu2+ and Pb2+ sorption and retention.In all the horizons Pb2+ exhibited greater hysteresis than Cu2+.In each soil the hysteresis in the A horizon was greater than that in the B horizon,except in the Bt horizon of the Endoleptic Luvisol,due to its high pH and vermiculite content.Based on migration indices,Pb2+ was less mobile than Cu2+ in the studied soils.  相似文献   

20.
Copper adsorption studies were conducted with 13 neutral to calcareous-alkaline soils. The data followed a Langmuir isotherm with two linear parts at low (part 1) and high (part 2) concentration of Cu in equilibrium solution. The ?pCu + 2pOH’? values show that part 1 and 2 stem largely from adsorption and precipitation reactions of Cu, respectively. The bonding energy and differential buffering capacity were significantly higher for part 1 while adsorption maximum and supply parameter were significantly higher for part 2 of the isotherms. Carbonate content, soil pH, organic matter, CEC and clay content were in that oder the predominant factors in elevating adsorption maximum, bonding energy coefficient and differential buffering capacity as well as decreasing supply parameter of soils. However, soil organic matter was the major determinant of strength of Cu adsorption. Copper potentials, adsorption maximum and differential buffering capacity were significantly correlated with dry matter production and Cu uptake in maize. The parameters of intensity factor predicted better the variation in yield and Cu uptake than the conventional soil test methods.  相似文献   

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