土壤、矿物质对60Co的吸附

研究了土壤、矿物质对60Co的吸附与水浸解吸.结果表明,(1)土壤、矿物质对60Co具有较强的吸附能力,饱和吸附率为68.6 %～97.1 %,分配系数为22～357 cm3/g;吸附率和分配系数大小顺序两者相同:硅藻土＞青紫泥＞红黄壤＞高岭土＞珍珠岩＞粉泥土.(2)60Co被土壤、矿物质吸附后不易解吸,解吸率1 %左右,大小顺序为红黄壤＞粉泥土＞高岭土＞珍珠岩＞青紫泥＞硅藻土.     

土壤,矿物质对^60Co的吸附

研究了土壤,矿物质对＾６０Ｃｏ的吸附与水浸解吸。结果表明,（１）土壤,矿物质对＾６０Ｃｏ具有较强的吸附能力,饱和吸附率为６８．６％－９７．１％,分配系数为２２－３５７ｃｍ＾３／ｇ;吸附率和分配系数大小顺序两者相同;硅藻土〉青紫泥〉红黄壤〉高岭土〉珍珠岩〉粉泥土。（２）＾６０Ｃｏ被土壤,矿物质吸附后不易解吸,解吸率１％左右,大小顺序内壤〉粉泥土〉高岭土〉珍珠岩〉青紫泥〉硅藻土。     

不同利用方式土壤中磷的吸附与解吸特性

研究不同利用方式土壤对磷的吸附解吸特性及其影响因素。采用室内恒温培养法研究了湖南典型土壤(红壤、潮土和紫色土)的不同利用方式(旱地、水田)土壤对P的吸附和解吸过程。土壤对磷的吸附解吸过程是分阶段进行的,用Langmuir方程拟合程度比Freundlich方程高,相关系数均在0.90(P<0.05)以上;从最大吸附量(Qm)、吸附反应常数(K)和最大缓冲容量(MBC)3项吸附参数综合考虑,旱地对P的吸附无论在强度还是容量方面均大于同母质的水田土壤;解吸率随着吸附量的增加而增大,其大小为旱地<水田。Qm与<0.002 mm粘粒及无定形铁含量呈正相关,相关系数分别为0.95和0.94(P<0.05)。不同利用方式土壤P吸附解吸特性差别较大,针对不同土壤应采取不同的磷素管理措施以实现作物增产和保护环境的双重效益。     

有机粘土和粘土对p,p''''-DDE的吸附/解吸研究

采用批量平衡实验,研究阳离子表面活性剂十六烷基三甲基铵离子(HDTMA)改性的zeo-HDTMA(有机沸石)、mont-HDTMA(有机蒙脱土)和atta-HDTMA(有机凹凸棒土)及其原粘土对典型有机氯农药DDT代谢产物p,p'-DDE的吸附解吸特性.结果表明,随原粘土阳离子交换容量(CEC)的增大,有机粘土吸附量增大,且有机粘土的吸附量比原粘土大大提高;有机粘土和原粘土对p,p'-DDE的吸附能力顺序为:zeo-HDTMA＞mont-HDTMA＞atta-HDTMA≥mont(蒙脱土)＞atta(凹凸棒土)＞zeo(沸石),这一顺序与它们的有机碳质量分数大小顺序一致.原粘土对p,p'-DDE的吸附等温线符合Langmuir吸附等温方程,吸附呈单分子层形式,且存在竞争吸附;有机粘土对p,p'-DDE的吸附等温线符合Linear吸附等温方程,吸附是p,p'-DDE在有机粘土中有机相的分配所致.当CaCl2质量浓度从0增加到50 g/L时,mont-HDTMA对p,p'-DDE吸附量提高了10.3%.有机粘土和原粘土对p,p'-DDE的解吸率大小顺序为:zeo＞atta＞mont＞atta-HDTMA＞mont-HDTMA＞zeo-HDTMA,这一顺序与它们的有机碳质量分数大小顺序相反.     

温度和表面活性剂对菲在土壤中吸附的影响

通过静态吸附实验,研究了北京地区土壤对菲的吸附行为,考察了温度和表面活性剂对菲吸附的影响.结果表明,6种土样对菲的吸附等温线均较好地符合Freundlich吸附模式,其吸附能力的大小顺序为:轻壤土>轻粘土>砂壤土>中壤土>重壤土>紧砂土;温度升高不利于菲在土壤中的吸附;十二烷基苯磺酸钠(LAS)和十六烷基三甲基澳化铵(CTAB)均利于菲在土壤表面的解吸,LAS和CTAB对菲的解吸率最高可达66.2%和31.8%,且LAS的解吸效果更好.     

pH和温度对2,2’,4,4’-四溴联苯醚在土壤中吸附和解吸行为的影响研究

研究了pH和温度对2,2’,4,4’-四溴联苯醚(BDE-47)在土壤中的吸附和解吸行为的影响。结果表明,pH和温度都可以影响BDE-47在受试土壤中的吸附和解吸行为。pH升高或降低均会使土壤对BDE-47的吸附能力提高,且在碱性环境中提高的程度更大;酸性或碱性条件下BDE-47在土壤中的解吸滞后性显著增强。温度降低后,土壤对BDE-47的吸附能力提高,5℃时的单点分配系数(Kd,表征土壤对BDE-47的吸附能力)是25℃时的1.03~1.67倍;温度由25℃降低到5℃后,BDE-47在土壤中的解吸滞后性增强。     

土壤对重金属的吸附

两价的重金属阳离子的吸附能力依赖于pH条件,当pH改变时吸附能力也随之改变.为了使金属产生同一本底,采用了大西洋沿岸的酸性底土,其对四种金属的吸附顺序为:Pb>Cu>Zn>Cd,其它土壤也具有同样的记载.但由于土壤种类不同且对金属的吸附性能也就不同.     

磺胺间甲氧嘧啶在土壤中的吸附/解吸特性研究

通过吸附/解吸动力学、吸附/解吸热力学试验研究了磺胺间甲氧嘧啶(SMM)在河南土壤上的吸附/解吸行为,并分析了影响SMM吸附/解吸的因素。结果表明,SMM在土壤中的吸附系数为18.9mL/g,土壤有机碳吸附系数为466.2mL/g,SMM在土壤中具有一定的移动性,对地下水和地表水存在一定的污染风险;描述SMM吸附过程的最优动力学方程为一级反应动力学方程,土壤对SMM的吸附近似于一级反应,且SMM在土壤中的吸附以物理吸附为主;用Freundlich方程来描述SMM在土壤的等温吸附行为最适宜,且SMM在土壤中的吸附经验常数的倒数均小于1,属于L-型吸附等温线。     

LAS对土壤中多环芳烃吸附行为的影响

研究了阴离子表面活性剂十二烷基苯磺酸钠(LAS)对PAHs在土壤中吸附行为的影响.结果表明,LAS改变了PAHs在土水体系中的吸附/解吸平衡,吸附态LAS可提高土壤对PAHs的吸附,而溶解态LAS则增加了PAHs的表观溶解度,这2种作用的综合结果改变了PAHs在土水体系中的吸附系数.因此,文中用表观吸附系数来描述PAHs在土壤-水-LAS体系中的综合吸附行为.     

4种人工湿地填料对磷的吸附特性分析

采用等温吸附、吸附动力学、填料饱和吸附后磷素释放实验,研究了紫色土、河沙、页岩、石灰岩对磷的吸附特征,结果表明Langmuir和Freundlich等温吸附方程均能很好地拟合各填料对磷的吸附特征,各填料对磷的最大吸附量大小顺序依次为石灰岩(666.67 mg/kg)河沙(500.00 mg/kg)页岩(434.78 mg/kg)紫色土(416.67 mg/kg);从反应速率来看,吸附过程都可分为快、中、慢3个阶段;相对一级动力学方程、双常数方程而言,Elovich方程对4种填料的吸附动力学特征拟合最好,决定系数R~2在0.831～0.966之间;从磷的解吸率来看,各填料释磷大小顺序依次为河沙(4.257%)页岩(3.803%)石灰岩(3.638%)紫色土(2.134%)。综合考察得出,石灰岩更适合作为人工湿地污水除磷的填料。     

Fate and mobility of pharmaceuticals in solid matrices

The sorption and mobility of six pharmaceuticals were investigated in two soil types with different organic carbon and clay content, and in bacterial biomass (aerobic and anaerobic). The pharmaceuticals examined were carbamazepine, propranolol, diclofenac sodium, clofibric acid, sulfamethoxazole and ofloxacin. The sorption experiments were performed according to the OECD test Guideline 106. The distribution coefficients determined by this batch equilibrium method varied with the pharmaceutical tested and the solid matrix type. Ofloxacin was particularly strongly adsorbed (except of the case of using anaerobic biomass for the solid matrix) while clofibric acid was found to be weakly adsorbed. The fate of pharmaceuticals in soil was also assessed using lysimeters. Important parameters that were studied were: the pharmaceutical loading rate and the hydraulic loading rate for adsorption and the rate and duration of a "rain" event for desorption. Major differences in the mobility of the six pharmaceuticals were observed and correlated with the adsorption/desorption properties of the compounds.     

Impact of sewage sludge spreading on nickel mobility in a calcareous soil: adsorption–desorption through column experiments

A soil column adsorption–desorption study was performed on an agricultural calcareous soil to determine the impact of sewage sludge spreading on nickel mobility. Ni adsorption experiments were followed by desorption tests involving the following liquid extractants: water, calcium (100 mg/L), oxalic acid (525 mg/L equivalent to 100 mg carbon/L), and sludge extracts (0.5 and 2.5 g/L). Desorption tests were also conducted after sewage sludge spreading at three application rates (30, 75, and 150 t/ha). According to the breakthrough curve, Ni adsorption was irreversible and occurred mainly through interactions with calcite surface sites. Nickel desorption from the soil column was promoted in presence of significant dissolved organic carbon (DOC) concentration as observed with oxalic acid elution and sludge extract at 2.5 g/L. In sludge-amended soil columns, the maximum Ni levels occurred in first pore volumes, and they were positively correlated to the sludge application rate. The presence of DOC in leaching waters was the main factor controlling Ni desorption from the sludge-amended soil columns. This finding implies that DOC generated by sludge applied on calcareous soils might facilitate the leaching of Ni due to the formation of soluble Ni–organic complexes. Thus, sludge application can have potential environmental impacts in calcareous soils, since it promotes nickel transport by decreasing Ni retention by soil components.     

Fate of nickel in a lime-stabilized biosolid,a calcareous soil and soil–biosolid mixtures

Soil contamination with anthropogenic metals resulting from biosolid application is widespread around the world. To better predict the environmental fate and mobility of contaminants, it is critical to study the capacity of biosolid-amended soils to retain and release metals. In this paper, nickel adsorption onto a calcareous soil, a lime-stabilized biosolid, and soil–biosolid mixtures (30, 75, and 150 t biosolid/ha) was studied in batch experiments. Sorption experiments showed that (1) Ni adsorption was higher onto the biosolid than the calcareous soil, and (2) biosolid acted as an adsorbent in the biosolid–soil mixtures by increasing Ni retention capacity. The sorption tests were complemented with the estimation of Ni adsorption reversibility by successive applications of extraction solutions with water, calcium (100 mg/L), and oxalic acid (equivalent to 100 mg carbon/L). It has been shown that Ni desorption rates in soil and biosolid-amended soils were lower than 30 % whatever the chemical reagent, indicating that Ni was strongly adsorbed on the different systems. This adsorption/desorption hysteresis effect was particularly significant at the highest biosolid concentration (150 t/ha). Finally, an adsorption empirical model was used to estimate the maximum permissible biosolid application rate using French national guideline. It has been shown that desorption effects should be quantitatively considered to estimate relevant biosolid loadings.     

Appendix

Abstract

The interaction of glyphosate [N‐(phosphonomethyl)‐glycine] with four typical European soils is reported. Results of adsorption and desorption isotherms show that the interaction of glyphosate with these soils was mainly related to content of iron and aluminium amorphus hydroxides. Moreover, it was found that the presence of divalent cations in 2: 1 clay minerals also contribute to glyphosate adsorption. The S‐type form of the adsorption isotherms revealed the existence of two different binding sites. These were exchangeable cations at low herbicide concentration and Fe and Al at higher glyphosate concentrations. The K maximum values of adsorption provided by the linear form of the Langmuir equation were found to be more consistent with soil parameters than those calculated by the Freundlich equation. The order of desorption from the soils was the reverse of that found for adsorption. Moreover, desorption varied from around 15 to 80% of the adsorbed herbicide according to the soil characteristics. This indicated that glyphosate adsorption on soils is far from being permanent and leaching to lower soil horizons with limited biological activity may occur.     

Some models for the adsorption kinetics of pesticides in soil

Abstract

Three models describing adsorption‐desorption kinetics of pesticides in soil, that could be incorporated into computer programs on pesticide movement in soil, were discussed, The first model involved single first‐order rate equations for adsorption and desorption. Results from an analytical and a numerical solution for local equilibration were compared. Concentration‐time relationships for the solution and adsorbed phases were calculated for different rate constants, initial conditions, and partition ratios at equilibrium. The second model described simultaneous adsorption‐desorption equilibration with two mechanisms, both with their own rate constants. After a comparatively fast equilibration with the first mechanism, there was a gradual increase in extent of overall‐adsorption, accompanied with a shift to greater amounts adsorbed by the second mechanism. With the third model, adsorption equilibration occurred by diffusion into a stagnant region. With diffusion distances ranging from 0.1 to 4.0 cm, the time needed for approach to adsorption equilibrium varied from about 0.25 days to about one year. Some of the possibilities of these models were discussed considering published experimental results.     

Sorptive behavior of the phenylamide fungicides,mefenoxam and metalaxyl,and their acid metabolite in typical Cameroonian and German soils

Laboratory soil sorption experiments were conducted on mefenoxam, formulated metalaxyl (F-metalaxyl), pure metalaxyl (P-metalaxyl) and metalaxyl acid metabolite to elucidate differences in their sorptive behaviour on typical Cameroonian forest soil (sand clay loam, pH 4.8 and 3.01% OC) and German soil (sandy loam, pH 7.2, 1.69% OC) using a batch equilibrium method. The data obtained on all test chemicals conformed to linear and Freundlich adsorption isotherms. The Langmuir equation failed to describe the sorption of the substances tested. All substances were adsorbed to a greater extent by the Cameroonian soil. The average percentage adsorptions for mefenoxam, F-metalaxyl, P-metalaxyl and the acid metabolite on the Cameroonian soil were 27.8%, 28.3%, 31.8% and 46.8% respectively while for the German soil they were 21.7%, 21.5%, 24.7% and 9.8% respectively. The KD and KF parameters and the Freundlich exponential term (1/n) were low, indicating that the interactions between soil particles and the fungicides were weak. The sorption parameters were lower in the German soil. P-metalaxyl exhibited a higher adsorption capacity than F-metalaxyl in both soils. Mefenoxam and F-metalaxyl exhibited similar sorption parameters in soils, whereas those of P-metalaxyl and acid metabolite differed. Differences observed in the adsorption between the two soils could be attributed to their properties. Desorption studies revealed that the adsorbed fungicides were not firmly retained by soil particles and their adsorption was reversible. Desorption of adsorbed mefenoxam, P-metalaxyl and of the acid metabolite from German soil was almost completely reversible with percentage desorption rates of more than 91.0%, whereas the rate for F-metalaxyl was 74.1%. All compounds exhibited some resistance to desorption from the Cameroonian soil, with percentage desorption rates less than 77.0%. Therefore if degradation in the soil is slow the fungicides described have a potential to leach to lower soil horizons.     

A comparison of five pesticides adsorption and desorption processes in thirteen contrasting field soils

Batch adsorption and desorption experiments were performed using thirteen agricultural soil samples and five pesticides. Experimental data indicated a gradient in pesticide adsorption on soil: trifluralin > 2,4-D > isoproturon> atrazine > bentazone. Atrazine, isoproturon and trifluralin adsorption were correlated to soil organic matter content (r2 = 0.7, 0.82, 0.79 respectively). Conversely, bentazone adsorption was governed by soil pH (r2 = 0.68) while insignificant effect has been shown in the case of 2,4-D. Multiple linear regressions were used to combine relationships between the various soil parameters and the Freundlich adsorption coefficient (K(f)) of each pesticide. Then desorption was assessed since it may reflect some of the interactions involved between the pesticides and the soil components. Adsorbed molecules were released into aqueous solution in the following order: bentazone > atrazine> isoproturon> 2,4-D > trifluralin. The occurrence of hysteresis did not allow an accurate interpretation of the pesticide desorption data because of the possible interplay of several processes.     

Sorption behavior of a new acidic herbicide in soils

The sorptive behavior of the experimental herbicide quinmerac (7-chloro-3-methyl-quinoline-8-carboxylic acid) was investigated in soils of different organic carbon content. Distribution coefficients are low (K_d = 0.03 - 12 mL g⁻¹) and are mainly determined by the soil organic carbon content. The adsorption mechanism operating in neutral to slightly acid agricultural soils is supposed to be cation bridging with the anionic form of quinmerac. Under acid conditions (pH 5.2) the predominating sorption mechanism is hydrophobic interaction. Therefore soil pH and cationic composition are also major factors determining the sorptive capacity of soils for quinmerac.

Adsorption kinetics, equilibrium adsorption and desorption isotherms were determined in batch experiments. Sorption kinetics were investigated at various times from 15 min to 96 hours. A two-step sorption behavior with time was found for the anionic form indicating two types of sorption mechanisms or sorption sites. Equilibrium for the first type was reached at a time-scale of minutes and for the second type after 24 hours. Adsorption isotherms were determined for two soil/solution ratios 1/5 and 1/3. Alteration of the adsorbent concentration exerted a strong influence on the adsorption isotherms. An increase of sorption was found with increasing adsorbent concentration. Under natural soil conditions sorption is therefore expected to be higher compared to the batch experiments. Desorption isotherms were obtained using the consecutive desorption method. Desorption hysteresis was not observed which indicates weak interactions. Implications of the results for the movement of quinmerac under field conditions and for models describing transport are discussed.     

An exploration of the relationship between adsorption and bioavailability of pesticides in soil to earthworm

A study was conducted to determine the adsorption/desorption of butachlor, myclobutanil and chlorpyrifos on five soils using a batch equilibration technique and to study the relationship between bioavailability to Allolobophora caliginosa and the adsorption/desorption of these three pesticides. The results showed that the adsorption/desorption processes of the tested compounds were mainly controlled by soil organic matter content (OM) and octanol/water-partitioning coefficient (K(ow)), and that the bioavailability of the pesticides was dependent on characteristics of pesticides, properties of soils, and uptake routes of earthworms. Bioconcentration of butachlor and myclobutanil was negatively correlated with Freundlich adsorption constant K(af) and K(df). However, only a slightly positive correlation between bioconcentration and K(af) and K(df) was observed for chlorpyrifos due to its high affinity onto soil.