Parameter optimization of the fungicide (Vapam) sorption onto soil modified with clinoptilolite by Taguchi method

This study employs the Taguchi optimization methodology to optimize the effective parameters for the pesticide (Vapam) sorption onto soil modified with natural zeolite (clinoptilolite). The experimental factors and their ranges chosen for determination of the effective parameters were: initial Vapam concentration (0.4–1.6 mg/L), initial pH of the pesticide solution (2–12), the percentage of clinoptilolite in the modified soil (0–6 %), temperature (15–35°C) and shaking time (2–24 h). The orthogonal array (OA) L₁₆ and the bigger the better response category of the Taguchi method were selected to determine the optimum conditions: initial Vapam concentration (1.2 mg/L), initial pH of the pesticide solution (2), the percentage of clinoptilolite in the modified soil (4 %), temperature (15°C) and shaking time (2 h). The results showed that in comparison with other parameters, the initial Vapam concentration was the most effective one for the sorption of this pesticide onto soil, modified with clinoptilolite. Moreover, after determining the optimum levels of the sorption process parameters, confirmation experiments were performed to prove the effectiveness of the Taguchi's experimental design methodology.     

Parameter optimization of the fungicide (Vapam) sorption onto soil modified with clinoptilolite by Taguchi method

This study employs the Taguchi optimization methodology to optimize the effective parameters for the pesticide (Vapam) sorption onto soil modified with natural zeolite (clinoptilolite). The experimental factors and their ranges chosen for determination of the effective parameters were: initial Vapam concentration (0.4-1.6 mg/L), initial pH of the pesticide solution (2-12), the percentage of clinoptilolite in the modified soil (0-6 %), temperature (15-35°C) and shaking time (2-24 h). The orthogonal array (OA) L(16) and the bigger the better response category of the Taguchi method were selected to determine the optimum conditions: initial Vapam concentration (1.2 mg/L), initial pH of the pesticide solution (2), the percentage of clinoptilolite in the modified soil (4 %), temperature (15°C) and shaking time (2 h). The results showed that in comparison with other parameters, the initial Vapam concentration was the most effective one for the sorption of this pesticide onto soil, modified with clinoptilolite. Moreover, after determining the optimum levels of the sorption process parameters, confirmation experiments were performed to prove the effectiveness of the Taguchi's experimental design methodology.     

过渡金属离子改性MCM-41对乙烯吸附的影响

为了提高吸附剂对乙烯气体的吸附量,对常见的MCM-41分子筛进行了过渡金属离子改性研究。通过镍离子交换实验,确定了改性条件,改性后的样品对乙烯的吸附行为发生改变。使用镍离子改性后的MCM-41在常温常压下对乙烯的最大吸附量为可达416cm3／g,约为商用颗粒活性炭的6倍,远高于其他文献的报道。吸附质的检测结果说明乙烯在其吸附过程中发生多聚反应,高碳数的直链烯烃为最终产物。CO原位红外吸附的引人证实经过热处理后,一价镍能在镍离子改性后的MCM-41样品中形成并成为乙烯聚合反应的活性中心。     

Influence of metal ion on sorption of p-nitrophenol onto sediment in the presence of cetylpyridinium chloride

Heavy metals and surfactants have a significant effect on the sorption of organic contaminants. In this study, batch equilibrium experiments were carried out to investigate the influence of Pb(NO(3))(2) on the sorption of p-nitrophenol (PNP) onto sediments in the presence of cationic surfactant cetylpyridinium chloride (CPC). Results indicated that in the complex system containing PNP, Pb(NO(3))(2) and CPC, the sorption of PNP decreased with increasing concentration of Pb(NO(3))(2) due primarily to competing for adsorption sites. Likewise, partitioning of PNP in adsorbed surfactant layers and micelles decreased with increasing level of Pb(NO(3))(2). Moreover, the influence of different metal ions (Pb(2+), Cd(2+), Zn(2+)) was examined and results indicated that the presence of heavy metals inhibited the sorption of PNP in the order: Pb(2+)>Cd(2+)>Zn(2+). The competitive effect of the heavy metals was in agreement with the hydration energy and hydrated radius. The results are believed to provide a useful insight into describing the transport and fate of PNP in natural environments.     

A Box-Behnken design for determining the optimum experimental condition of the fungicide (Vapam) sorption onto soil modified with perlite

In the present study, response surface methodology (RSM) based on the Box-Behnken design (BBD) was employed to investigate the effects of the different operating conditions on the removal of the fungicide (Vapam) onto soil modified with perlite using sorption process. The process parameters such as pH of the fungicide solution (2, 5 and 8), temperature (15, 25 and 35°C), shaking time (2, 13 and 24 h) and the percentage of perlite in the modified soil (0, 2 and 4 %) were investigated using a four-factor-three-level Box-Behnken design at an initial fungicide concentration of C(0) = 1.6 mg/L as a fixed input parameter. A second-order quadratic model suggested the optimum conditions to be as follows: fungicide solution pH of 3.57, temperature of 15°C, shaking time of 3.5 h and 4% of perlite in the modified soil which resulted in the improvement of Vapam sorption. Under optimum conditions, the fungicide (Vapam) removal was predicted 12.88 μg/g by BBD. The confirmatory experiments were conducted and the results revealed that the fungicide removal was 13.14 μg/g which indicated that the predicted and the observed values of response (Vapam removal) were in close agreement. Therefore, the soil modified with perlite holds good potential for Vapam sorption. This is the first report on fungicide Vapam sorption onto soil modified with perlite using statistical experimental design employing response surface methodology.     

A Box-Behnken design for determining the optimum experimental condition of the fungicide (Vapam) sorption onto soil modified with perlite

In the present study, response surface methodology (RSM) based on the Box-Behnken design (BBD) was employed to investigate the effects of the different operating conditions on the removal of the fungicide (Vapam) onto soil modified with perlite using sorption process. The process parameters such as pH of the fungicide solution (2, 5 and 8), temperature (15, 25 and 35°C), shaking time (2, 13 and 24 h) and the percentage of perlite in the modified soil (0, 2 and 4 %) were investigated using a four-factor-three-level Box-Behnken design at an initial fungicide concentration of C₀ = 1.6 mg/L as a fixed input parameter. A second-order quadratic model suggested the optimum conditions to be as follows: fungicide solution pH of 3.57, temperature of 15°C, shaking time of 3.5 h and 4% of perlite in the modified soil which resulted in the improvement of Vapam sorption. Under optimum conditions, the fungicide (Vapam) removal was predicted 12.88 μg/g by BBD. The confirmatory experiments were conducted and the results revealed that the fungicide removal was 13.14 μg/g which indicated that the predicted and the observed values of response (Vapam removal) were in close agreement. Therefore, the soil modified with perlite holds good potential for Vapam sorption. This is the first report on fungicide Vapam sorption onto soil modified with perlite using statistical experimental design employing response surface methodology.     

改性木屑对铜离子的吸附性能

用热解+NaOH浸泡的方法制备改性木屑,通过表征手段观察了改性后木屑表面结构的变化,并研究了改性木屑对水溶液中Cu2+的吸附性能。结果表明：改性木屑表面变光滑,羟基增多;与原木屑和活性炭相比,改性木屑的平衡时间缩短了60 min,吸附速率提高了50%;改性木屑对铜离子的吸附符合Langmuir等温模型,最大吸附量为31.25 mg·g-1,是原始木屑吸附量的8倍,是活性炭的3倍。     

Nonequilibrium sorption of phenols onto geosorbents: the impact of pH on intraparticle mass transfer

While the pH effect on sorption equilibrium of weak acids on natural sorbents was investigated in a number of studies, less is known about the pH dependence of sorption kinetics. This paper investigates the impact of pH on sorption kinetics during the transport of some selected phenols through a sandy aquifer material. Breakthrough curves measured in column experiments were analyzed using a mass transfer based nonequilibrium model designated as dispersed flow, film and particle diffusion model (DF-FPDM). In this model, the rate limiting intraparticle diffusion is characterized by the mass transfer coefficient, kSaV, which can be determined from breakthrough curves by curve fitting. The experimental results indicate that the kSaV is pH-dependent and inversely correlated with the pH-dependent distribution coefficient, K(d,app). Regression equations are presented that may be used to estimate approximate values of intraparticle mass transfer coefficients on the basis of experimentally determined or LFER predicted distribution coefficients.     

Removal of perfluorinated surfactants by sorption onto granular activated carbon, zeolite and sludge

Perfluorinated surfactants are emerging pollutants of increasing public health and environmental concern due to recent reports of their world-wide distribution, environmental persistence and bioaccumulation potential. Treatment methods for the removal of anionic perfluorochemical (PFC) surfactants from industrial effluents are needed to minimize the environmental release of these pollutants. Removal of PFC surfactants from aqueous solutions by sorption onto various types of granular activated carbon was investigated. Three anionic PFC surfactants, i.e., perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonate (PFBS), were evaluated for the ability to adsorb onto activated carbon. Additionally, the sorptive capacity of zeolites and sludge for PFOS was compared to that of granular activated carbon. Adsorption isotherms were determined at constant ionic strength in a pH 7.2 phosphate buffer at 30 degrees C. Sorption of PFOS onto activated carbon was stronger than PFOA and PFBS, suggesting that the length of the fluorocarbon chain and the nature of the functional group influenced sorption of the anionic surfactants. Among all adsorbents evaluated in this study, activated carbon (Freundlich K(F) values=36.7-60.9) showed the highest affinity for PFOS at low aqueous equilibrium concentrations, followed by the hydrophobic, high-silica zeolite NaY (Si/Al 80, K(F)=31.8), and anaerobic sludge (K(F)=0.95-1.85). Activated carbon also displayed a superior sorptive capacity at high soluble concentrations of the surfactant (up to 80 mg l(-1)). These findings indicate that activated carbon adsorption is a promising treatment technique for the removal of PFOS from dilute aqueous streams.     

天然和巯基改性沸石吸附水溶液中重金属Hg2+的特征研究

为了提高沸石对汞的吸附性,利用半胱胺盐酸盐对天然斜发沸石进行改性,制得巯基改性沸石。研究了吸附剂用量、pH值、温度、Hg²⁺浓度和吸附时间对沸石和巯基改性沸石吸附Hg²⁺的影响,并进一步研究了吸附机理。结果表明,巯基改性沸石吸附Hg²⁺受pH值、温度的影响较小,吸附机制主要是沸石表面的硫与Hg²⁺的化学反应。而天然沸石对Hg²⁺的吸附主要是离子交换作用,受温度、pH值等的影响较大,随温度的升高吸附量下降。整个吸附过程以较快的速度进行。天然沸石在吸附时间为1 h、巯基改性沸石在0.5 h时基本达到吸附平衡。吸附条件试验和Langmuir等温吸附模型都表明,巯基改性沸石对Hg²⁺的吸附能力得到了很大的提高,吸附容量由8.06 mg/g 提高到19.88 mg/g,提高了146.65%。     

天然和巯基改性沸石吸附水溶液中重金属Hg^2＋的特征研究

为了提高沸石对汞的吸附性,利用半胱胺盐酸盐对天然斜发沸石进行改性,制得巯基改性沸石。研究了吸附剂用量、pH值、温度、Hg^2＋浓度和吸附时间对沸石和巯基改性沸石吸附Hg^2＋的影响,并进一步研究了吸附机理。结果表明,巯基改性沸石吸附Hg^2＋受pH值、温度的影响较小,吸附机制主要是沸石表面的硫与Hg^2＋的化学反应。而天然沸石对Hg^2＋的吸附主要是离子交换作用,受温度、pH值等的影响较大,随温度的升高吸附量下降。整个吸附过程以较快的速度进行。天然沸石在吸附时间为1h、巯基改性沸石在0．5h时基本达到吸附平衡。吸附条件试验和Langmuir等温吸附模型都表明,巯基改性沸石对Hg^2＋的吸附能力得到了很大的提高,吸附容量由8．06mg／g提高到19．88mg／g,提高了146．65％。     

聚苯胺修饰电极去除水中高氯酸根

在三电极体系中,研究聚苯胺修饰电极对高氯酸根离子的电化学去除。基于导电高聚物的电控离子交换特性,在其电化学扫描过程中高氯酸根能够掺杂进入到聚苯胺高分子链。在0.10 mol/L Na2SO4 (pH 4.0)电解液中电化学循环伏安扫描25 min,2 mg/L高氯酸根的去除率达96.5%;在相同处理时间内,去除率随高氯酸根浓度的增加而明显降低,且溶液pH在3到5的范围内得到最优的去除效果。通过红外光谱和X射线光电子能谱表征高氯酸根掺杂前后的聚苯胺膜,结合循环伏安图的分析提出高氯酸根去除过程中可能的反应机理:高氯酸根作为掺杂离子,随电位的改变在聚苯胺链中迁移。研究表明,基于聚苯胺的电控离子交换特性,可以开发一种绿色高效的高氯酸根去除技术。     

Prediction of the adsorption capacity for volatile organic compounds onto activated carbons by the Dubinin-Radushkevich-Langmuir model

Prediction of the adsorption capacity for volatile organic compounds (VOCs) onto activated carbons is elucidated in this study. The Dubinin-Radushkevich (D-R) equation was first used to predict the adsorption capacity of nine aromatic and chlorinated VOCs onto two different activated carbons. The two key parameters of the D-R equation were estimated simply from the properties of the VOCs using quantitative structure-activity relationship and from the pore size distribution of the adsorbent. The approach based on the D-R equation predicted well the adsorption capacity at high relative pressures. However, at the relative pressures lower than -1.5 x 10(-3), the D-R approach may significantly overestimate adsorption capacity. To extrapolate the approach to lower relative pressures, the integration of the D-R equation and the Langmuir isotherm, called the D-R-L model, was proposed to predict adsorption capacity over a wide range of relative pressures of VOCs. In this model, the Langmuir isotherm parameters were extracted from the predicted D-R isotherm at high relative pressures. Therefore, no experimental effort was needed to obtain the parameters of the D-R-L model. The model successfully predicted the adsorption capacity of aromatic and chlorinated hydrocarbons tested onto BPL and Sorbonorit B carbons over relative pressures ranging from 7.4 x 10(-5) to 0.03, suggesting that the model is applicable at the low relative pressures of VOCs often observed in many environmental systems. In addition, the molecular size of organic compounds may be an important factor affecting the adsorption capacity of activated carbons. For BPL carbon, an ultramicroporous adsorbent, the limiting pore volume Wo of the D-R equation decreased when the kinetic diameter of the adsorbate was larger than 6 angstroms. However, for Sorbonorit B carbon, no reduction of Wo was found, suggesting that the Wo may be related to the pore size distribution of the adsorbents, as well as to their molecular size. This size exclusion effect may play an important role in predicting the adsorption capacity of VOCs onto microporous adsorbents in the D-R-L model and in the corresponding D-R equation.     

Enhancement of phosphorus sorption onto light expanded clay aggregates by means of aluminum and iron oxide coatings

Phosphorus (P) loading from non-point or point sources increases the eutrophication risk of natural waters. The functioning of constructed wetlands (CWs) used as natural water treatment systems can be improved by means of additional materials adsorbing soluble P. In this study, light expanded clay aggregates (LECA) and LECA coated with aluminum (Al) oxide (Al-LECA) or iron (Fe) oxide (Fe-LECA) were tested for their efficiency as P sorbents in the pH range 3–8. The oxide coatings duplicated the actual sorption capacity calculated from the sorption isotherms at the P concentration in the equilibrium solution of 20 μg L⁻¹, assumed to be the allowable P level in purified water. In the oxide-coated LECAs the sorption was fast and followed both the first- and second-order Lagergren kinetic models, suggesting that the formation of a binuclear surface complex was feasible. In LECA, sorption was markedly slower and followed the first-order kinetic model, indicating that retention occurred through a monodentate attachment. These findings were in harmony with the degree of P saturation (DPS) of the sorbent surfaces at the highest P addition level (200 μg L⁻¹), DPS being decisively higher for LECA than for the oxide-coated sorbents. Accordingly, at higher pH values the competition by hydroxyl ions diminished the sorption in LECA relatively more than that in the coated sorbents. In agreement with the acidity of Al³⁺ being 100 times lower than that of Fe³⁺, at elevated pH the sorption by Al-LECA proved to be less reversible than that by Fe-LECA. The results provide evidence that in CWs Al-coated sorbents are superior to Fe-coated ones that are also redox-sensitive and may lose their sorption properties in anoxic conditions.     

偶联剂改性凹凸棒土处理含汞(Ⅱ)废水的研究

利用一种含氮硅烷偶联剂γ-氨丙基三乙氧基硅烷改性凹凸棒土,对凹凸棒土改性前后的表面性质进行了分析,并通过静态吸附实验研究了材料对水中汞离子的吸附性能.研究结果表明,酸活化增加了凹凸棒土吸附材料的孔道直径,使吸附速度加快,30 min即达到吸附平衡.通过硅烷偶联剂对凹凸棒土的改性,在材料表面引入了大量氨基,提高了材料对汞...     

离子交换法改性的NaY分子筛对吸附含硫VOCs的性能提升

为解决分子筛在含湿条件下对小分子含硫VOCs吸附性能差的问题,并实现高效捕集,采用液相离子交换法选取不同金属离子 (Ag、Cu、Mg、Zn、Ce、Ca等) 对NaY和USY-3分子筛进行改性,以二甲基硫醚 (DMS) 作为模型物,考察2种改性分子筛对高湿度含硫VOCs脱除效果,进而优选性能优异的改性分子筛,再通过多组分VOCs竞争吸附实验来模拟实际应用效果。结果表明,NaY和USY-3分子筛改性后均可保持结构稳定,NaY型分子筛较USY-3分子筛具有更高的离子交换容量,改性后吸附性能提升更明显,CuY、AgY分子筛的DMS吸附性能优异 (CuY的穿透吸附量为203 mg·g⁻¹,AgY的穿透吸附量为132 mg·g⁻¹) 。然而,仅有Ag离子交换可提高NaY分子筛的抗水性,在1.5%水蒸气存在时,DMS穿透吸附量最高可达99 mg·g⁻¹,且5次循环再生后吸附容量仍在90%。在对二甲苯 (PX) 存在时,分子筛对2种VOCs的吸附量均高于80 mg·g⁻¹,且DMS具有绝对的竞争吸附优势。本研究表明AgY分子筛具有优异的抗水性和吸附选择性,可为其在含湿条件下对VOCs中小分子硫化物的吸附净化应用提供参考。     

Studies on the phosphorus sorption capacity of substrates used in constructed wetland systems

Langmuir sorption isotherm was used to screen various substrates for use in removing phosphorus (P) in constructed wetlands (CW). The nine tested substrates included four sands, two soils, bentonite, and two industrial by-products of furnace slag and fly ash. Results showed that the furnace slag had the highest P sorption capacity (8.89 g Pk g(-1)), followed was the fly ash (8.81 g P kg(-1)), and that of sand II was the lowest. Different kinds of sands also showed varying P sorption capacity (0.13-0.29 g P kg(-1)). P sorption capacity was influenced by both the physico-chemical characteristics of the substrates and the amount of organic matter (OM) added. Lifetime of sand II for P sorption estimated by Langmuir P sorption maximum was up to only 9 months in full-scale systems, while that of furnace slag could be used for up to 22 yr. Furnace slag has great potential as a CW substrate, due to its high P sorption capacity. The expected lifetime of constructed wetlands for P removal is strongly influenced by the choice of adsorbing substrate.     

Enhancement of sorption capacity of cocoa shell biomass modified with non-thermal plasma for removal of both cationic and anionic dyes from aqueous solution

Environmental Science and Pollution Research - Removal of cationic dye, Azur II, and anionic dye, Reactive Red 2 (RR-2) from aqueous solutions, has been successfully achieved by using a modified...     

Physical origin for the nonlinear sorption of very hydrophobic organic chemicals in a membrane-like polymer film

Bioconcentration factor (BCF) is often assumed to be linearly associated with the octanol-water partition coefficient K(ow) for hydrophobic organic chemicals (HOCs). However, a large amount of data has suggested that the correlation between the logBCF and logK(ow) is curvilinear for HOCs. Similar curvilinear relationship has also been noticed for sorption of HOCs into poly(dimethyl)siloxane (PDMS), a polymer with cross-linked interior structures. So far no satisfactory explanation has been given to account for the deviation. In this study, we acquired additional experimental data to show that the curvilinear relationship between the log-based PDMS-coated fiber-water partition coefficient (logK(f)) and logK(ow) for polychlorinated biphenyls (PCBs) was indeed a reflection of the sorption process occurring in PDMS film other than experimental defects. The physical origin of the nonlinearity was pinpointed based on the theory of phase partitioning for HOCs. The linear relationship is observed if the solute molecule is considerably smaller than the size of a monomer unit of PDMS in that the Gibbs free energy required for cavity formation in PDMS is comparable to that in octanol. Higher free energy of cavity formation is needed to create sufficient free volume if the PCB molecular size is comparable to or larger than the monomer unit of PDMS. On the other hand, the free energy of cavity formation in octanol remains almost constant when this occurs, resulting in the observed curvilinear relationship. The proposed model adequately explains the observed data, as well as sheds lights into the physical origin of the steric interactions of large molecular size solute with the PDMS polymer network.