1，2-二氯苯在3种基质中的吸附研究

采用平衡振荡法研究了1,2-二氯苯在3种人工湿地基质中的吸附情况。结果表明,1,2-二氯苯在12 h达到吸附平衡,可由Lagergren一级吸附动力学模型得出3种土壤的吸附速率常数分别为0.3338 h-1、0.2679 h-1和0.2537 h-1,壤土的吸附效果明显好于细砂、粗砂。30℃的吸附等温线既符合Freud...     

4种人工湿地基质对马拉硫磷的吸附特性

通过基质对马拉硫磷的等温吸附和吸附动力学实验,研究天然土壤、煤渣、沸石、砾石对马拉硫磷的吸附特性,为人工湿地处理含马拉硫磷废水提供理论依据.结果表明:马拉硫磷浓度为2.25 ～ 90 mg/L条件下,Langmuir和Freundlich方程均能较好地拟合4种基质对马拉硫磷的等温吸附过程,并且Freundlich方程的拟合效果要好于Langmuir方程.马拉硫磷的理论饱和吸附量大小依次为天然土壤(9.9304 mg/g)＞煤渣(1.6173 mg/g)＞沸石(0.6039 mg/g)＞砾石(0.3965 mg/g).4种基质对马拉硫磷的缓冲能力大小依次为天然土壤＞煤渣＞沸石＞砾石,即当进水马拉硫磷浓度波动较大时,作为湿地基质天然土壤使人工湿地系统维持稳定出水水质的能力最强.马拉硫磷浓度为4.5 mg/L条件下,吸附动力学模型Elovich方程能较好地拟合4种基质对马拉硫磷的吸附动力学特征,说明4种基质对马拉硫磷的吸附是表面吸附和内部扩散吸附共同作用的结果.因此,天然土壤和煤渣适宜作为处理含马拉硫磷废水的人工湿地基质.     

垂直流人工湿地中基质组合对污水的处理效果及模型模拟

选择石砾、粗砂、细砂作为垂直流人工湿地的基质在实验室内研究不同粒径的基质在不同的水力负荷和对不同浓度污水对污染物的去除效果,根据实验结果选取基质应用于示范基地,利用人工湿地模型Subwet2.0对人工湿地示范基地进行模型模拟,为农村生活污水人工湿地系统的处理设计及模拟出水水质提供参考。研究结果表明:石砾、粗砂、细砂为基质对污染物去除率较好的水力负荷分别为小于0.9、0.6和0.3 m/d时;石砾基质对COD的最佳污染负荷为970 mg/L,粗砂、细砂基质为468~970 mg/L;粗砂和细砂基质对NH4+-N去除效果相似;在北方地区垂直流人工湿地主体基质建议使用粗砂或石砾以减少堵塞的风险;利用Subwet2.0模型模拟人工湿地示范基地的出水水质,根据当地条件在反应参数的取值范围内调整了相应的参数值,模拟的结果符合性很高。     

模拟煤灰渣垂直潜流人工湿地的除磷性能分析

为确定煤灰渣作为垂直潜流人工湿地基质的可行性,通过静态吸附实验和煤灰渣去除生活污水中的磷素实验,表明煤灰渣对污水中磷素的吸附平衡时间较短,吸附速率较快.当温度降低时,煤灰渣的磷素吸附容量对吸附平衡浓度依赖性和吸附强度随之降低,最大理论吸附容量亦降低 83.10% .在处理0.5 m 3 /(m2·d)的生活污水中,煤灰渣对TP的平均去除率达86.03%,吸附方式包括物理吸附和化学吸附,同时得出煤灰渣最大磷素解析量占最大理论吸附容量的0.73%,在实际人工湿地应用中应注意磷素解析而形成的二次污染.     

加气混凝土砌块吸附初期径流中磷的效果与机制

为发掘具有高效除磷性能的新型基质,提高人工湿地处理初期径流能力。选用废弃的加气混凝土砌块（加气块）作为实验材料,通过吸附动力学、吸附等温线实验及磷形态分析实验等探究其对磷的吸附机制,并将其作为基质应用于人工湿地中处理初期降雨径流,与传统基质砾石作对比,考察湿地除磷效果。结果表明：吸附过程随时间呈现快速吸附、缓慢平衡的特点,且可用准二级动力学方程拟合;吸附过程中溶液的pH、Ca2+浓度均随时间增加而升高;Langmuir吸附等温方程相较于Freundlich可更好地描述加气块对磷的等温吸附过程,最大吸附容量（Qm）为4 170.71 mg·kg-1;吸附主要是以Ca-P形式的化学吸附,且不易解吸。加气块湿地除磷效果明显优于砾石湿地。因此,将加气块应用于湿地处理初期经流,能有效提高湿地除磷能力。     

3种人工湿地基质对磷的吸附特性

选用页岩、陶粒和砾石3种基质进行等温吸附和吸附动力学试验,研究其对磷的吸附特性。结果表明,Freun-dlich和Langmuir方程均能较好地拟合各基质对磷的吸附特征,并且用Freundlich方程的拟合效果要好于Langmuir方程;基质对磷的理论饱和吸附量大小依次为页岩(527.992 mg/kg)>陶粒(328.165 mg/kg)>砾石(129.729 mg/kg);页岩最大磷吸附量随粒径增加而减小;各基质对磷的吸附过程分为快、中、慢3个阶段,3种基质对磷的吸附速率依次为页岩>陶粒>砾石;准二级动力学方程、双常数方程和Elovich方程均能较好地描述人工湿地基质对磷的吸附动力学特征,但从相关系数来看,准二级动力学方程的描述更为准确。     

多环芳烃在淮河、黄河和卫河沉积物上的吸附及解吸行为研究

以淮河沉积物上多环芳烃的吸附研究为主线,以黄河、卫河沉积物为比对,研究菲和芘在3种河流沉积物上的吸附和解吸行为,重点考察吸附剂有机质组分、环境温度、吸附时间和共存物等因素对吸附的影响,找出可以用来预测这3条河流沉积物对多环芳烃吸附作用的模式。结果表明,菲和芘在3种河流沉积物上的吸附均呈非线性,可用Freundlich方程拟合,属放热反应、物理吸附。同一吸附质的有机碳归一化分配系数(Koc)数值相近,说明吸附剂有机质组分对吸附起主导作用;吸附能力随着吸附时间延长而增加,并与吸附质疏水性成正比;多环芳烃共存,有竞争吸附现象;辛醇/水分配系数可用来预测3种河流沉积物对多环芳烃的吸附作用;解吸存在滞后现象,吸附质疏水性强、吸附剂有机质含量高的体系,解吸滞后现象更加明显。     

土壤颗粒级配对镉吸附-解吸规律的影响

利用甘肃金川某地土壤通过批实验进行等温吸附和动力学解吸实验,研究不同颗粒级配的中砂对镉的吸附、解吸特征,并采用Freundlich和一级动力学方程对其吸附解吸方程进行拟合。结果表明,(1)Freundlich和一级动力学方程对该土壤吸附、解吸镉的实验适用;(2)等温吸附实验中4组不同颗粒级配的中砂对镉的吸附性很强,最大平衡吸附量依次为260.667、286.107、299.362和292.232 mg/kg,吸附性能与颗粒级配中的细粒土相对含量大小成正比;(3)4组土壤对镉的解吸在初期2 h内解吸速率均较快,在3 h左右达到吸附-解吸平衡。平衡后4组土样Ⅰ、Ⅱ、Ⅲ和Ⅳ的最大解吸量依次为0.752、0.561、0.44和0.54 mg/kg,解吸速率和平衡时最大解吸量均与颗粒级配中细颗粒相对含量密切相关。     

3种人工湿地基质对邻苯二甲酸二丁酯的吸附特性

通过湿地基质对邻苯二甲酸二丁酯（DBP）的吸附动力学和等温吸附实验,对比天然土壤、沸石、陶粒对DBP的吸附特性,作为人工湿地处理含DBP废水的理论依据。结果表明,DBP浓度在30~1 000 μg·L-1时,Freundlich比Langmuir模型更好地模拟出各湿地基质对DBP的吸附特征。3种基质对DBP的饱和吸附量大小：土壤（0.065 5 mg·g-1）> 沸石（0.016 4 mg·g-1）> 陶粒（0.013 7 mg·g-1）。3种基质对DBP的缓冲能力大小依次为土壤 > 陶粒 > 沸石,即当人工湿地进水的DBP浓度变化较大时,土壤可以很好地维持出水水质,土壤很适合作为处理含DBP废水的人工湿地基质。DBP浓度为600 μg·L-1时,双常数模型能很好地拟合3种基质对DBP的吸附动力学特征。     

含水层介质对Cr(VI)的吸附特征

结合天津典型地质和Cr(VI)污染情况,选择细砂、中砂、粗砂这3种含水层介质作为研究对象,研究其对Cr(VI)的吸附动力学实验和等温吸附实验。研究结果表明:3种含水层介质对Cr(VI)的吸附均包括2个阶段——快速吸附阶段和缓慢吸附阶段,并在2 h时达到吸附平衡,符合Elovich型吸附动力学。含水层介质对Cr(VI)的等温吸附模型符合Freundlich模型,表明吸附过程以不均匀吸附为主。含水层介质对Cr(VI)的吸附能力由大到小的顺序依次为细砂、中砂、粗砂;且当Cr(VI)溶液的初始浓度为0.1 mg/L,含水层介质为10 g细砂时,达到最大吸附率22.67%,吸附率很低,表明这3种含水层介质不易吸附Cr(VI),也就说明Cr(VI)进入地下水后不易被含水层介质吸附截留,而是在地下水中随之流动,造成远距离污染。     

As(V) retention on soils and forest by-products and other waste materials

As(V) retention capacity is determined by means of adsorption/desorption trials performed for coarse and fine ground mussel shell, forest and vineyard soils with or without fine shell, pine wood ash, oak wood ash, pine sawdust and slate-processing fines. Pine ash shows the highest arsenic retention potential (with >97 % adsorption and ≤1 % desorption), followed by shell-amended forest soil (adsorption between 96 and 92 %), by un-amended forest soil (adsorption between 98 and 86 %) and by the amended vineyard soil (adsorption between 92 and 75 %). Sawdust is the material with the lowest arsenic retention capacity in most cases, with un-amended vineyard soil also showing poor results. In the case of oak ash, As(V) percentage adsorption becomes higher with increasing added arsenic concentrations, while this increase in added arsenic causes lower percentage adsorption in the case of slate fines. Regarding adsorption ability, As(V) adsorption data were fitted to Freundlich and Langmuir models, showing good fitting, with pine ash and shell-amended forest soil having the highest K _F values. In view of that, mussel shell amendment would be useful to increase arsenic retention on forest and vineyard soils, while pine ash could be used to retain arsenic even from wastewaters.     

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。     

Adsorption behavior of RH‐5992 insecticide onto sandy and clay loam forest soils

Abstract

Adsorption‐desorption behavior of RH‐5992 [Mimic®, N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine] in sandy and clay loam forest soils was studied using the batch equilibrium method. Adsorption was higher in the clay loam soil than in the sandy loam, and increased linearly with RH‐5992 concentration, but decreased with increasing pH and temperature. The adsorption data fit better to the Freundlich, than to the Langmuir equation. The K_D (linear adsorption constant) and K_F (Freundlich constant) were similar for each soil at 5, 15 and 25°C and decreased with increase of temperature, indicating that the enthalpy of adsorption was negative. The exponent of the Freundlich equation was close to unity for both soils at all three temperatures. The low E_a (energy of activation) indicated a diffusion‐controlled process during the initial stages of adsorption. The desorption isotherm differed from that of adsorption, and the linear desorption constant, K_D(d), was ca 25 times higher than the K_D, indicating that adsorption of RH‐5992 was not readily reversible. Evaluation of thermo‐dynamic parameters confirmed the presence of strong bonds between the solute and soil. These findings suggest that RH‐5992 has a limited potential for downward mobility leading to groundwater contamination.     

Sorptive interactions and binding of δ‐endotoxin protein from bacillus thuringiensis subsp. kurstaki inforest soils

Abstract

The adsorption, desorption and binding of the insecticidal protein from Bacillus thuringiensis subsp. kurstaki (Btk toxin) onto autoclaved sandy and clay loam forest soils were studied at 23°C in a buffer medium (pH 10.2) using the precipitated protein mixture (active + inactive) obtained from a commercial Btk formulation. The active protein in the buffer solution was quantified by ELISA technique. Maximum adsorption of the toxin onto the sandy (301 μg/g) and clay (474 μg/g) loam soils was found to occur after 3 and 4 hours of agitation, respectively. Adsorption of the toxin was higher in the clay loam soil than in sandy loam. Adsorption parameters were calculated using the Freundlich and linear isotherm equations. The K_F and 1/n values for the soils were 1.12 and 1.48 (sandy), and 20.42 and 0.874 (clay), respectively, indicating stronger affinity of the toxin for the clay compared to the sandy loam soil. The linear model showed deviations at higher concentrations, nevertheless using the best fit, K_D and K_OC values were computed for the two soils. For sandy loam, the K_D and K_OC values were 9.38 and 391, respectively; the corresponding values for clay loam were 13.19 and 425, confirming the higher sorption affinity of the toxin for clay loam. The adsorption data did not fit the Langmuir equation because of heterogeneity of the soil surface. Desorption studies showed that more than half of the adsorbed toxic protein remained firmly attached to sandy (162.6 μg/g or 54.5%) and clay (314.0 μg/g or 67.4%) loam soils after six 0.5‐h washes (total 3.0 h wash time). Although the toxin appears to be a non‐leacher, its lateral mobility, soil persistence and biological consequences, including bioavailability of the bound residues, are poorly understood and require further investigation.     

Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15–92%, whereas with the Kota fly ash an increase in sorption by 13–38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K_f/K_d values, K_FA values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

Tylosin Sorption to Silty Clay Loam Soils,Swine Manure,and Sand

The objectives of this study were to assess sorption and desorption of tylosin, a macrolide antimicrobial chemical used in swine, cattle, and poultry production, in three silty clay loam soils of South Dakota and compare soil sorption to sand and manure sorption. The silty clay loam soils, from a toposequence in eastern South Dakota, standardized sand samples, and swine manure were used in 24-h batch sorption studies with tylosin concentrations ranging from 25 to 232 μ mole/L. Desorption from soil was conducted over a four-day period. Partition coefficients, based on the Freundlich isotherm (K _f ) or K _d values, were calculated. K _f values for the silty clay loams were similar, not influenced by landscape position, and averaged 1350 with isotherm slopes ranging from 0.85 to 0.93. K _f values for sand were dependent on solution/sand ratios and pH, ranging from 1.4 to 25.1. K _d values of manure were dependent on the solution type and ranged from 840 L/kg with urine to about 175 L/kg when sorbed from water. Desorption of tylosin from each soil over the four-day period was < 0.2% of the amount added. The soils' high K _f values and low desorption amounts suggest that once tylosin is in these soils, leaching to lower depths may not occur. However, this does not preclude runoff with soil eroded particles. If tylosin reaches a sand aquifer, through bypass flow or other mechanism(s), movement in the aquifer most likely would occur.     

Adsorption-desorption and leaching of pyraclostrobin in Indian soils

Pyraclostrobin is a new broad-spectrum foliar applied and seed protectant fungicide of the strobilurin group. In this paper, adsorption-desorption of pyraclostrobin has been investigated in three different soils viz. Inceptisol (sandy loam, Delhi), Vertisol (sandy clay, Hyderabad) and Ultisol (sandy clay loam, Thrissur). Effect of organic matter and clay content on sorption was also studied in Inceptisol of Delhi. Leaching potential of pyraclostrobin as influenced by rainfall was studied in intact soil columns to confirm the results of adsorption-desorption studies. The adsorption studies were carried out at initial concentrations of 0.05, 0.1, 0.5, 1 and 1.5 μg mL^?1. The distribution coefficient (K_d) values in three test soils ranged from 4.91 to 18.26 indicating moderate to high adsorption. Among the three test soils, adsorption was the highest in Ultisol (K_d 18.26), followed by Vertisol (K_d 9.87) and Inceptisol (K_d 4.91). K_F value was also highest for Ultisol soil (66.21), followed by Vertisol (40.88) and Inceptisol (8.59). S-type adsorption isotherms were observed in all the three test soils. K_d values in organic carbon-removed soil and clay-removed soil were 3.57 and 2.83 respectively, indicating lower adsorption than normal Inceptisol. Desorption studies were carried out at initial concentrations of 0.5, 1 and 1.5 μg mL^?1. Desorption was the greatest in Inceptisol, followed by Vertisol and Ultisol. Amounts of pyraclostrobin desorbed in three desorption cycles for different concentrations were 23.1–25.3%, 9.4–20.7% and 8.1–13.6% in Inceptisol, Vertisol and Ultisol respectively. Desorption was higher in clay fraction-removed and organic carbonremoved soils than normal Inceptisol. Desorption was slower than adsorption in all the test soils, indicating hysteresis effect (with hysteresis coefficient values varying from 0.05 to 0.20). Low values of hysteresis coefficient suggest high hysteresis effect indicating easy and strong adsorption, and slow desorption, of pyraclostrobin in soils. Higher hysteresis coefficient values in organic carbon removed soil (0.25–0.30) and clay fraction removed soil (0.28–0.36) as compared to normal Inceptisol soil suggest relatively weak adsorption and easy desorption of pyraclostrobin. Results of regression analysis suggest that the organic matter and pH of the soil play a major role in adsorption of pyraclostrobin. Leaching studies were carried out in intact soil columns in Inceptisol. The columns were leached with different amounts of water simulating different amounts of rainfall. The results suggest that most of the pyraclostrobin residues will remain present in the top soil layers even under high rainfall conditions and chances of pyraclostrobin moving to lower soil depth are almost negligible.     

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。     

Sorption of alpha and beta hydrophobic endosulfan in a Vertisol from southeast region of Turkey

Endosulfan has been applied to control numerous insects in a variety of food and non-food crops. Limited information is available on dynamics of this pesticide in the soil. The objective of this research was to determine the adsorption–desorption behavior of the alpha (α) and beta (β) endosulfan in a Vertisol from the southeast region of Turkey, where cotton is the main crop in the large irrigated lowlands. The α and β endosulfan were adsorbed considerably and Freundlich adsorption–desorption isotherms fitted the α and β endosulfan data (R² > 0.98). Freundlich adsorption coefficients (K_f) for the α endosulfan ranged between 21.63 and 16.33 while for the β endosulfan they were between 14.01 and 17.98 for the Ap and Bw2 horizons. The difference of K_f values of α and β endosulfan for two horizons were explained with the slight difference in the amount of organic matter and clay, but considerable difference in Fe contents of the two horizons. Alpha and β endosulfan K_fd values were 118.03 and 45.81 for the Ap and 48.08 and 68.71 for the Bw2 horizons. Higher adsorption and desorption behavior of the endosulfan isomers for the same horizon was attributed to poor physical bonding between the endosulfan molecule and the surfaces of fundamental soil particles. This fact is thought to increase the effective use of endosulfan in agriculture with a possibility of its movement to the surface and groundwater in the Vertisol studied.     

ADSORPTION–DESORPTION,PERSISTENCE, AND LEACHING BEHAVIOR OF DITHIOPYR IN AN ALLUVIAL SOIL OF INDIA

Investigations were undertaken to determine the adsorption–desorption, persistence and leaching of dithiopyr (S,S′-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoromethyl pyridine-3,5-dicarbothioate) in an alluvial soil under laboratory condition. The adsorption–desorption studies were carried out using batch equilibration technique. The mass balance studies showed that 83–97% of the pesticide was recovered during adsorption–desorption studies. The results revealed strong adsorption of dithiopyr in alluvial soil with K_d values ranging from 3.97–5.78 and Freundlich capacity factor (K_F) value of 2.41. The strong adsorption was evident from the hysteresis effect observed during desorption. The hysteresis coefficients ranged from 0.17–0.40.

The persistence studies were carried out at two concentrations (1.0 and 10.0 μg g^?1 level) under field capacity moisture and submerged condition by incubating the treated soil at 25±1°C. In general, dithiopyr persisted beyond 90 days with half-life varying from 11.5–12.9 days under different conditions. The rate of application and moisture regimes had no overall effect on the persistence. The leaching studies carried out in packed column under saturated flow condition revealed that dithiopyr was highly immobile in alluvial soil. Only small amounts (0.02–0.04%) were recovered from leachate whereas major portion (99.9%) remained in top layer of the soil column. The data suggest that strong adsorption of dithiopyr will cause a greater persistence problem in the soil. However, the chances of its movement to ground water will be negligible due to its immobility.