纳米粘土矿物对阿特拉津的吸附-解吸特性研究

采用批量平衡实验,研究了纳米粘土矿物与原粘土矿物对除草剂阿特拉津的吸附解吸特陛。结果表明,粘土矿物对阿特拉津的吸附-解吸均能用Freundlich方程很好地拟合。随着溶液中阿特拉津浓度的增加,粘土矿物对阿特拉津的吸附量增加;粘土矿物粒径越小,吸附量越大,纳米粘土矿物的吸附量显著大于原粘土矿物。粘土矿物对阿特拉津吸附量大小顺序为：纳米SiO2）纳米蒙脱石〉凹凸棒石〉蒙脱石〉SiO2。粘土矿物对阿特拉津的解吸表现出一定的滞后效应,即粘土矿物吸附的阿特拉津越多,解吸的越少。粘土矿物对阿特拉津的解吸率大小顺序为：SiO2〉凹凸棒石〉纳米蒙脱石〉纳米SiO2〉蒙脱石。     

无定型氧化铁对土壤中阿特拉津吸附-解吸的影响

选取人工合成的无定型氧化铁(AHOsFe)纯矿物,以及两种典型土壤(黑土和砖红壤)的原土(S1和S2)和AHOsFe包被土壤(AHOsFe-S1和AHOsFe-S2)为研究材料,采用批量平衡法,研究AHOsFe对土壤中阿特拉津(AT)吸附—解吸行为的影响及其机理。研究结果表明,各吸附剂对AT的吸附均能采用Freundlich方程进行较好地拟合(r≥0.996,p0.01),AHOsFe对AT具有较强的吸附性能和较高的吸附非线性,AHOsFe包被黑土和砖红壤后,两种土壤对AT的吸附能力(Kd值)分别增加56.3%和43.8%。各吸附剂对AT均存在解吸迟滞效应,两种土壤及被AHOsFe包被后,其对AT的解吸迟滞系数(HI)在AT低初始浓度时随浓度的增加而降低,而在AT高初始浓度时随浓度的增加略有增加,AHOsFe对AT的HI则随AT初始浓度的增加而增加,说明不同吸附剂在AT不同初始浓度时的解吸迟滞机制不同。与土壤相比,AHOsFe对AT具有较强的解吸迟滞效应,但AHOsFe包被土壤后,却降低了土壤对AT的解吸迟滞效应。     

土壤矿物和胡敏酸对阿特拉津的吸附-解吸作用研究

选取了6种土壤矿物(蒙脱石、高岭石、钙饱和处理蒙脱石、钙饱和处理高岭石、无定型氧化铁和无定型氧化铝),以及从土壤中提取纯化的3种胡敏酸为材料,采用批量吸附平衡法,研究土壤矿物和胡敏酸对阿特拉津的吸附特性。结果表明,各吸附剂对阿特拉津的吸附均能采用Frundlich方程进行较好地拟合(r≥0.982,p0.01)。胡敏酸对阿特拉津具有最大的吸附性能,其固-液分配系数(Kd值)随平衡浓度(Ce值)的变化基本恒定,吸附等温线呈线性(Frundlich方程常数N≈1),吸附以分配溶解作用为主,吸附可逆性较高。黏土矿物(特别是蒙脱石)对阿特拉津也具有较强的吸附能力,Kd值随Ce值增加而增加,吸附等温线呈S型(N1),吸附主要是通过表面亲水作用。无定型氧化铁铝的Kd值随Ce值增加而降低,当Ce达到一定水平后,Kd趋于恒定,吸附等温线呈L形(N1),吸附主要是通过无定型氧化物表面的羟基与阿特拉津分子间的化学键合作用,吸附可逆性最差。     

菲在土壤/沉积物上的吸附-解吸过程及滞后现象的研究

实验研究了菲在土壤 /沉积物上的吸附 解吸过程。CHL土壤和HFH沉积物中有机质的固相13 CCPMASNMR谱图很相似 ,表明样品中有机质的组成差异不大 ;菲在土壤 /沉积物上的吸附过程表现出明显的非线性 ;线性模型不适合拟合菲的吸附等温线 ,Freundlich模型和双区位反应模型 (DRDM)较好地拟合了菲的吸附等温线 ,其中DRDM模型还清楚地反映菲在低浓度和高浓度下不同的吸附方式 ;另外 ,研究表明菲在土壤 /沉积物上的解吸过程中存在明显的滞后现象 ,这可能和土壤 /沉积物有机质的异质性和土壤胶团微小孔隙的存在有关。     

不同温度下镉在典型农田土壤中的吸附动力学特征

按土重的3%和5%向采自海南和广西的3种可变电荷土壤中添加由稻草制备的生物质炭,混合培养30 d后用一次平衡法研究了生物质炭对土壤吸附Cd（Ⅱ）的影响及其与土壤表面电化学性质的关系,旨在阐明生物质炭促进可变电荷土壤吸附和固定Cd（Ⅱ）的机制。结果表明,添加稻草炭显著提高了3种土壤的阳离子交换量（CEC）和土壤pH,并使土壤胶体Zeta电位向负值方向位移。因此,添加稻草炭增加了土壤表面的负电荷量,土壤表面对Cd（Ⅱ）的吸附容量增强,使3种可变电荷土壤对Cd（Ⅱ）的吸附量增加,且Cd（Ⅱ）吸附量的增幅随稻草炭添加水平的提高而增加。Freundlich方程和Langmuir方程可以拟合3种土壤对Cd（Ⅱ）的吸附等温线,但Freundlich方程拟合效果更好,该方程表征吸附容量的常数k也随着稻草炭添加水平提高而增大。研究表明在pH3.0~5.0范围内,稻草炭均增加土壤对Cd（Ⅱ）的吸附量。添加稻草炭提高土壤pH,促进Cd（Ⅱ）的吸附,因为Cd（Ⅱ）的吸附量随pH升高而增加。解吸实验表明,添加稻草炭处理Cd（Ⅱ）的解吸量高于对照处理,说明生物质炭提高了土壤对Cd（Ⅱ）的静电吸附量。     

稻草生物质炭对3种可变电荷土壤吸附Cd（Ⅱ）的影响

按土重的3%和5%向采自海南和广西的3种可变电荷土壤中添加由稻草制备的生物质炭,混合培养30 d后用一次平衡法研究了生物质炭对土壤吸附Cd（Ⅱ）的影响及其与土壤表面电化学性质的关系,旨在阐明生物质炭促进可变电荷土壤吸附和固定Cd（Ⅱ）的机制。结果表明,添加稻草炭显著提高了3种土壤的阳离子交换量（CEC）和土壤pH,并使土壤胶体Zeta电位向负值方向位移。因此,添加稻草炭增加了土壤表面的负电荷量,土壤表面对Cd（Ⅱ）的吸附容量增强,使3种可变电荷土壤对Cd（Ⅱ）的吸附量增加,且Cd（Ⅱ）吸附量的增幅随稻草炭添加水平的提高而增加。Freundlich方程和Langmuir方程可以拟合3种土壤对Cd（Ⅱ）的吸附等温线,但Freundlich方程拟合效果更好,该方程表征吸附容量的常数k也随着稻草炭添加水平提高而增大。研究表明在pH3.0~5.0范围内,稻草炭均增加土壤对Cd（Ⅱ）的吸附量。添加稻草炭提高土壤pH,促进Cd（Ⅱ）的吸附,因为Cd（Ⅱ）的吸附量随pH升高而增加。解吸实验表明,添加稻草炭处理Cd（Ⅱ）的解吸量高于对照处理,说明生物质炭提高了土壤对Cd（Ⅱ）的静电吸附量。     

对硝基氯苯在土壤和腐殖酸上的长期吸附与多步解吸的研究

采用批量平衡实验法研究了对硝基氯苯（p-NCB）在土壤和腐殖酸上的长期吸附和多步解吸,比较了连续的多步解吸与一步解吸的差异。结果表明,随着吸附时间的增加吸附量均会有所增加,随吸附时间增加吸附等温线的非线性增强。p-NCB在液相和固相上的初始浓度对吸附速率有一定影响,低浓度比高浓度时达到平衡的速率要低。对于两种受试土壤,两次解吸得到的等温线均无法与吸附等温线重合,表现出很强的吸附不可逆性。而尽管p-NCB在腐殖酸上表现出明显的非线性吸附（n = 0.794）,但4次解吸后所得到的平衡位点与吸附所得的平衡位点基本落在同一条直线上,对数坐标下进行线性拟合的相关系数（R2）可达0.988,说明吸附过程是完全可逆的。     

名山河流域黄壤组分对微团聚体吸附解吸镉的影响

选取名山河流域4种土地利用方式（林地、水田、茶园、旱地）的黄壤为研究对象,采用平衡液等温吸附法和NH4OAC、EDTA溶液解吸法,研究土壤组分（有机质、游离氧化铁）对微团聚体吸附解吸Cd2＋的影响。结果表明：去除土壤组分前后,原土及各粒径微团聚体对Cd2＋的吸附量均随Cd2＋初始浓度增大而增大,吸附量均按以下次序递减：（〈0.002mm）〉2～0.25mm〉原土〉0.053～0.002mm〉0.25～0.053mm,与有机质、游离氧化铁、CEC呈极显著正相关。吸附减少量大小关系为：去除有机质〉去除游离氧化铁,有机质的贡献率大于游离氧化铁。Freundlich方程拟合效果最佳,达到极显著水平,分布系数Kd值与Cd2＋初始浓度呈曲线负相关。NH4OAC解吸率随原吸附Cd2＋初始浓度增大而增大,以最大解吸率计,递减规律为：0.25～0.053mm〉0.053～0.002mm〉原土〉2～0.25mm〉（〈0.002mm）;EDTA解吸率随原吸附Cd2＋初始浓度增大而减小,递减规律与NH4OAC解吸率相反。去除土壤组分后,NH4OAC解吸率上升,EDTA解吸率下降,茶园与旱地黄壤非解吸率减小,林地与水田黄壤非解吸率增大。去除土壤组分后,非专性吸附与吸附总量呈极显著正相关,专性吸附与吸附总量呈极显著负相关。     

毒死蜱有毒代谢物3,5,6-TCP在土壤中的吸附-解吸研究

应用OECD106批平衡方法,研究了毒死蜱的有毒代谢物3,5,6-TCP在6种典型土壤中的吸附-解吸行为。结果表明：Elovich方程、双常数方程和抛物线扩散方程能较好地拟合3,5,6-TCP在第四纪红土、黑土、黄壤和褐土中的吸附动力学过程,而对紫色土和潮沙土的拟合度较低（拟合相关系数小于0.85）;应用Freundlich方程和线性方程拟合第四纪红土、黑土、黄壤和褐土的经验常数nfads均小于1（非线性吸附）,而紫色土和潮沙土的nfads值则接近于1（线性吸附）;3,5,6-TCP在6种土壤中解吸的滞后系数H值均大于1,即解吸速率大于吸附速率。6种土壤对3,5,6-TCP的吸附常数Kfads从1.37-6.74μg1-n·fmLn·fg^-1,吸附系数Kd值从0.50-1.30mL·g^-1,其中第四纪红土和黑土对其吸持力较强（Kd〉1）,因而更应注意环境安全;其他4种土壤的Kd值则均小于1,淋溶风险较大。     

四环素在土壤中的吸附与解吸以及镉在其中的影响

采用批平衡实验方法,研究了四环素（TC）在褐土和红壤中的吸附和解吸,以及Cd2＋对四环素在两种土壤上吸附和解吸的影响。结果表明,四环素在褐土和红壤中的吸附可以用Freundlich等温吸附方程拟合,所得lgKf分别为3.039和3.169,这表明四环素在红壤中的吸附能力较强。此外,四环素在两种土壤上的解吸过程都存在滞后现象,所得lgKf,des分别为3.292和3.877,这将可能威胁到土壤环境和人体健康。常见重金属Cd2＋的存在会促进四环素在两种土壤上的吸附,在红壤中表现显著（P〈0.05）;同时红壤中四环素的lgKf,des有所增加,而在褐土中的变化不大。     

Adsorption-desorption of atrazine on four soils of Hyderabad

The adsorption-desorption equilibrium of atrazine (2-chloro, 4-ethylamino, 6-isopropyl amino-1, 3, 5 triazine) was studied by the batch equilibration method at 27 ± 1 °C on four soils of Hyderabad. Adsorption isotherms conformed to the Freundlich equation (A = KC^1/n ). K increased in the same order as the organic C content of the soils. Desorption studies were conducted by repeated replacement of 5 mL of the supernatant equilibrium solutions after adsorption, with 0.01 M CaCl₂. Desorption isotherms showed considerable hysteresis which was more prominent when the desorption was carried out with higher adsorbed concentration of atrazine. Desorption from the lowest level of adsorbed atrazine (3 to 5 μg g^?1 soil) was close to the adsorption isotherm. The cumulative desorption after four desorption steps covering five days was significantly different at the 1% level, for different initial adsorbed concentrations of atrazine. Desorption was significantly higher at the lowest adsorbed level of atrazine. The soils differed significantly at 6% level for desorption and the amount desorbed decreased in the inverse order of organic C. Desorption isotherms also conformed to Freundlich equation but K andn values were both higher than that for adsorption and increased with increase in initially adsorbed concentration of atrazine. Desorption thus confirmed the irreversible nature of the adsorption of atrazine on these soils. The quantitative factors and reasons for desorption are discussed.     

Influence of humic acid on adsorption and desorption of atrazine, hydroxyatrazine, deethylatrazine, and deisopropylatrazine onto a clay-rich soil sample

Adsorption and desorption properties of atrazine and some of its metabolites, hydroxyatrazine (AT-OH), deethylatrazine (DEA), and deisopropylatrazine (DIA), were studied with a clay-rich soil sample (clay content of 53%). A part of this soil was treated with humic acid (Soil-HA) to assess the influence of this important component of natural organic matter on adsorption and desorption processes. This study was performed using the batch approach with 1.0 g of soil, or Soil-HA, in 5.0 mL of 0.010 mol L(-)(1) CaCl(2) solution containing the herbicide and the metabolites in a concentration range between 0.010 and 5.0 mg L(-)(1). After 24 h of contact time, the suspensions were centrifuged and the four compounds were quantified in the supernatant phases by high-performance liquid chromatography. The adsorption and desorption data of both Soil and Soil-HA were properly fitted by the linearized Freundlich equation. For the untreated soil, the adsorption affinity order evaluated as a function of the K(f) values was AT-OH > AT > DIA > DEA, while desorption followed the order DEA > DIA approximately AT > AT-OH. The presence of humic acid increased significantly the adsorption of all compounds, following the same affinity order observed for the untreated soil. Increase in adsorption was especially high for AT-OH and AT. On the other hand, the dealkylated metabolites, DEA and DIA, were more easily desorbed from the Soil-HA sample, suggesting that natural organic matter facilitates the leaching of these compounds. Desorption order in the presence of humic acid was DEA > DIA > AT > AT-OH.     

Cu^2＋、Zn^2＋复合条件下Cd^2＋在陕西5种土壤中的吸附

通过平衡吸附的方法,研究了Cd2＋在单一及与Cu2＋、Zn2＋复合条件下,在陕西塿土、黄绵土、黑垆土、黄褐土、砂土5种土壤中的吸附特征,并通过多重相关分析探讨了其吸附机制。结果表明,在20、30℃条件下,Cd2＋在各供试土样中吸附等温线总体上呈H或L型等温线形式,黑垆土对Cd2＋总是吸附最强,而砂土的吸附总是最弱;Cd2＋吸附的温度效应呈现升温负效应特征,塿土土样中,Cu2＋的共存对其温度效应影响较大,而在其他4种土样中Zn2＋的共存具有较大影响;Cu2＋、Zn2＋的共存均降低了Cd2＋的吸附量,具有显著的拮抗作用;Freundlich模型是描述Cd2＋吸附等温线最佳模型。相关分析结果表明,Cd2＋在土壤中的吸附主要以电性引力吸附为主,Cu2＋的共存主要和其与土壤有机质之间的络和吸附等化学吸附作用有关,因此其对Cd2＋以化学竞争性吸附的影响相对较弱,而Zn2＋共存吸附与Cd2＋吸附机制类似,因此表现出Zn2＋共存对Cd2＋吸附影响较大的特点。     

Movement,adsorption and mineralization of atrazine in two soils with and without switchgrass (Panicum virgatum) roots

A study was conducted to determine the influence of switchgrass roots on the mobility, adsorption–desorption and mineralization of atrazine in Cullen clay loam and Emporia loamy sand soils. Bromide and atrazine distribution profiles in the leachates indicated greater preferential movement in columns with roots than in columns without roots. Larger concentrations of atrazine were detected at lower depths of Emporia soil with switchgrass roots than without. Adsorption of atrazine was greater in Cullen than in Emporia soil and conformed to Freundlich isotherms. In both Cullen and Emporia soils, adsorption and desorption were not different between soil with or without switchgrass roots. After 84 days of incubation, less than 6% of the applied atrazine was mineralized in the Cullen soil and 2% in Emporia soil. Mineralization was greater in the Cullen soil than in the Emporia soil at 42, 56, 70 and 84 days of sampling. The presence of switchgrass roots did not affect the mineralization of atrazine in Emporia soil. The presence of switchgrass roots caused preferential movement of atrazine, but did not affect its adsorption and mineralization in either soil type.     

Quantifying effects of primary parameters on adsorption–desorption of atrazine in soils

Purpose

Adsorption and desorption are important processes that influence the transport, transformation, and bioavailability of atrazine in soils. Equilibrium batch experiments were carried out to investigate the adsorption–desorption characteristics of atrazine. The objectives of this study were to (1) determine and quantify the main soil parameters governing atrazine adsorption and desorption phenomena; (2) find the correlativity between the identified soil parameters; and (3) investigate the universal desorption hysteresis traits.

Materials and methods

Fifteen soils with contrasting physico-chemical characteristics were collected from 11 provinces in eastern China. The equilibrium time was 24 h both for adsorption and desorption experiments. Atrazine was detected by Waters 2695/UV HPLC.

Results and discussion

Adsorption isotherms of atrazine could be well described by the Freundlich equation (r?≥?0.994, p?<?0.01). The total organic carbon (TOC) was the first independent variable that described 53.0 % of the total variability of K _f, followed by the pH (9.9 %), and the clay (4.0 %) and silt (1.2 %) contents, separately; while the primary soil properties that affect desorption parameters included the TOC, pH, free Fe₂O₃ (Fe_d) and the sand content, with the biggest contribution achieved by the TOC (ranged from 48.5–78.1 %). The results showed that when the content ratio of clay to TOC (RCO) was less than 40, the atrazine adsorption was largely influenced by the organic matrix, while when the RCO was greater than 40, they were vital affected by the clay content.

Conclusions

Adsorption–desorption isotherms of atrazine in soils were nonlinear. The content of TOC, clay, and iron oxides, as well as the pH value were the key soil parameters affecting the adsorption–desorption of atrazine in soil, among which the RCO especially exhibited relevance. Additionally, the desorption hysteresis existed for atrazine retention in all 15 tested soils, and the hysteretic effect enhanced with the increasing time for desorption. This would be ascribed to the heterogeneity physical–chemical properties of these soils.     

Zur statistischen Abhängigkeit der Adsorption verschiedener Herbizidwirkstoffe vom Anteil der organischen Substanz in Böden

On the relation of herbicide adsorption and soil organic fraction Freundlich adsorption isotherms were measured for four herbicides (atrazine, terbuthylazine, chlorotoluron, isoproturon) and 24 soil horizons, which are typical of Schleswig-Holstein, northern Germany. The relationship between the adsorption constant (K_Fr) of a chemical and the fraction of organic carbon (f_OC) of the soil horizons was evaluated. Chemical specific K'_OC-values, that are independent of soil organic carbon fraction varied considerably for each herbicide (CV about 50%); therefore these values as well as K_OC-values, that are determined by linear regression of K_Fr and f_OC should be evaluated critically before application. K'_OC- and K_OC-values derived from experiments showed decreasing affinity of the herbicides to soil horizons in the order terbuthylazine > chlorotoluron > atrazine ? isoproturon. Calculation of K_OC from K_OW or water solubility of each herbicide, however, led to changes in the above mentioned ranking. Hence, especially K_OW or water solubility based K_OC-values may lead to false conclusions concerning chemical mobility. For atrazine, terbuthylazine and isoproturon Freundlich adsorption constants increased overproportionally with increasing organic carbon content of soils. The relationships between K_Fr and f_OC therefore were described better by a non-linear equation (second order polynom) than by a linear approach. Contrary, for chlorotoluron a linear relation between K_Fr and f_OC holds at least for the range of f_OC investigated in this study.     

富啡酸对石灰性潮土中磷吸附-解吸及其对锌次级吸附-解吸的影响

通过吸附和解吸试验,研究了富啡酸（Fulvic acid,FA）对石灰性潮土中磷吸附一解吸的影响,并进行了吸附富啡酸和磷后对锌次级吸附一解吸的影响。结果表明：同时吸附不同磷和富啡酸后,土壤对磷的吸附量随磷初始浓度的增加而增加,而随富啡酸吸附初始浓度的增加而降低;石灰性潮土磷等温吸附曲线用Langumir方程式描述时,土壤对磷的吸附反应常数K、最大吸附量Xm、最大缓冲容量KxXm均随富啡酸初始浓度的增加而降低;KNO_3、KOH、HCI对吸附磷的解吸量所占比例及磷的总解吸量均随富啡酸浓度的增加而增加。土壤对Zn^2＋的吸附率随磷和富啡酸吸附初始浓度的增加而降低;而其解吸率随磷和富啡酸吸附浓度的增加而增加,说明磷和富啡酸减少了土壤对Zn^2＋的吸附,且增加了其在土壤中的解吸量。所以,石灰性潮土中富啡酸提高了土壤中磷的有效性,而且磷和富啡酸提高石灰性土壤中锌的有效性。