Lead(II) and cadmium(II) removal from aqueous solution using processed walnut shell: kinetic and equilibrium study

The biosorption potential of processed walnut shell for Pb(II) and Cd(II) ions from aqueous solutions was explored. The effects of pH, contact time, initial ion concentration, and amount of dried adsorbent were studied in batch experiments. The maximum adsorption was achieved within the pH range 4.0–6.0. The equilibrium data were well fitted by the Langmuir isotherm model. The maximum monolayer adsorption capacities were found to be 32?g?kg^?1 and 11.6?g?kg^?1 for Pb(II) and Cd(II) ions, respectively. Kinetic data were best described by the pseudo-second-order model. The structural features of the adsorbent were characterized by Fourier transform infrared spectroscopy, which confirmed the involvement of hydroxyl (–OH), carboxyl (–COO^–), and carbonyl (C=O) groups in metal sorption. This readily available adsorbent is efficient in the uptake of Pb(II) and Cd(II) ions from an aqueous solution and could be used for the treatment of wastewater streams bearing these metal ions.     

森林新近凋落叶溶出DOM的性质及其对菲增溶作用的影响

凋落叶作为森林凋落物的主要组成部分,其溶出的大量有机质也是森林土壤可溶性有机质（DOM）的主要来源之一。研究森林凋落叶溶出DOM对PAHs增溶作用的影响有利于合理预测及评价森林土壤中PAHs的环境行为和生态风险。本研究采集了南亚热带常绿阔叶人工林的4种常见树种--尾叶桉（Eucalyptus urophylla）、木荷（Schima superba）、大叶相思（Acacia auriculiformis）和湿地松（Pinus elliottii）的新近凋落叶为试验材料,研究其DOM含量、组成与性质,对比分析了不同凋落叶DOM对菲的増溶作用及其与DOM性质的相关关系。结果表明,4种凋落叶的可溶性有机碳（DOC）质量分数在C 11.61~36.25 mg·g-1之间,其中尾叶桉的含量最大,湿地松最小。尾叶桉和木荷DOM的主要组分是可溶性糖（SS）和可溶性酚（SP）,两者总C量占DOC的比例超过47%,而大叶相思和湿地松中SS和SP两者总量所占比例均低于30%。另外,4种凋落叶DOM的质量分数（以C计）与其电导率的线性关系图中有明显转折点,说明它们均具有表面活性剂的性质。凋落叶DOM在临界胶束浓度（CMC）之上对菲具有不同程度的増溶作用,其与菲的结合系数（logKDOC）的大小顺序为尾叶桉（3.05 L·kg-1）＞木荷（3.02 L·kg-1）＞大叶相思（2.79 L·kg-1）＞湿地松（2.54 L·kg-1）,这表明尾叶桉和木荷DOM的增溶作用明显高于大叶相思和湿地松DOM。经分析表明,logKDOC与各DOM在254、280 nm处的特征紫外吸光度值（SUV-A254、SUV-A280）及其SS、SP的相对含量均呈显著正相关（p＜0.01）,与A240/A420、A254/A400比值呈显著负相关（p＜0.01）,说明DOM的芳香化程度越高,分子量越大, SS与SP所占比例越高,其对菲的増溶效果越明显。     

热液中金的沉淀机理研究综述

金的沉淀机理是了解热液金矿床成矿机制的关键。本文总结了金从热液中沉淀机理的最新研究成果，介绍了各种主要含金配合物的溶解度拨制机制，阐述了矿物表面吸附／还原以及电化学富集等矿物表面作用对金沉淀行为的制约。     

Reversibly enhanced aqueous solubilization of volatile organic compounds using a redox-reversible surfactant

Surfactant-enhanced remediation (SER) is an effective method for the removal of volatile organic compounds (VOCs) from contaminated soils and groundwater. To reuse the surfactant the VOCs must be separated from the surfactant solutions. The water solubility of VOCs can be enhanced using reversible surfactants with a redox-acive group, (ferrocenylmethyl)dodecyldimethylammonium bromide (Fcl2) and (ferrocenylmethyl)tetradecanedimethylammonium bromide (Fcl4), above and below their critical micelle concentrations (CMC) under reducing (I⁺) and oxidative (I²⁺) conditions. The CMC values of Fcl2 and Fcl4 in I⁺ are 0.94 and 0.56 mmol/L and the solubilization of toluene by Fcl2 and Fcl4 in I⁺ for toluene is higher than the solubilization achieved with sodium dodecyl sulfate, cetyltrimethylammonium bromide and Trition X-114. The solubilization capacity of the ferrocenyl surfactants for each tested VOCs ranked as follows: ethylbenzene > toluene > benzene. The solubilities of VOCs by reversible surfactant in I⁺ were 30% higher than those in I²⁺ at comparable surfactant concentrations. The effects of Fcl4 concentrations on VOCs removal efficiency were as follows: benzene > toluene > ethylbenzene. However, an improved removal efficiency was achieved at low ferrocenyl surfactant concentrations. Furthermore, the reversible surfactant could be recycled through chemical approaches to remove organic pollutants, which could significantly reduce the operating costs of SER technology.     

Photolysis of the herbicide bispyribac sodium in aqueous medium under the influence of UV and sunlight in presence or absence of sensitizers

The photolysis of a rice herbicide Bispyribac sodium (Sodium 2, 6-bis [(4, 6-dimethoxypyrimidin-2-yl) oxy] benzoate) has been studied in different aqueous medium (distilled water, pond water and Irrigation water) under the influence of UV (λ max ≥ 250 nm) and sunlight in presence or absence of sensitizers (TiO₂ and KNO₃). The study was conducted under laboratory simulated condition which made it possible to evaluate the contribution of different factors viz. source of irradiation, solvent and sensitizers towards the photolysis of bispyribac sodium. The photodegradation proceeds via first order reaction Kinetics in all the cases. Five photo metabolites (M₁-M₅) were isolated in pure form by column chromatographic method from the irradiation system under UV influenced and TiO₂ as sensitizer. From the different spectral data (IR, NMR, UV-VIS, Mass) the structure of these five metabolites were assigned as M₁ (Phenol), M₂ [2, 6-Dihydroxy benzoic acid], M₃ [2, 6-bis [(4, 6 dimethoxypyrimidin-2yl) oxy] benzoic acid], M₄ [2-(3-Hydroxy-phenoxy)-pyrimidine-4, 6-diol] and M₅ as [2,4-Dihydroxy-3, 5-dimethoxy-6-(4-methoxy pyrimidine-2-yloxy)-benzoic acid]. Moreover, another six photometabolites (M₆-M₁₁) were identified from the different irradiation system on the basis of Micromass analysis. On the basis of MS/MS data analysis, the structure of these six photometabolites were assigned as M₆ [2-(4, 6-Dimethoxy-pyrimidin-2-yloxy)-6-hydroxy-benzoic acid], M₇ [2-Hydroxy-6-(4-hydroxy-6-methoxy-pyrimidin-2-yloxy)-benzoic acid], M₈ [4, 6-Dimethoxy-pyrimidin-2-ol], M₉ [6-Methoxy-pyrimidine-2, 4-diol], M₁₀ [2-Hydroxy-6-(pyrimidin-2-yloxy)-benzoic acid] and M₁₁ [2, 4, 6-Trimethoxy-pyrimidine]. The plausible Photodegradation pathways of bispyribac sodium in the present investigation were portrayed which proceeds via hydrolysis, hydrolytic cleavage, O-dealkylation, decarboxylation, dehydroxylation, O-alkylation and hydroxylation.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs)     

Leaching,mobility and persistence of tebufenozide in columns packed with forest litter and soil

Abstract

Leaching, downward mobility and persistence of tebufenozide was investigated under laboratory conditions in columns packed with forest litter and soil, after fortification with the analytical grade material (purity > 99.6%) and with two commercial formulations, RH‐5992 2F (aqueous flowable) and RH‐5992 ES (emulsion suspension). Two types of litter and soil were used: one type with relatively high amounts of sand and the other with high amounts of clay.

The concentrations eluted in the leachates were lower when the analytical material (dissolved in acetone) was used for fortification, than when the two formulations (diluted with water) were used. The amount leached was higher for RH‐5992 2F than for RH‐5992 ES. The type of substrate, i.e., sandy or clay type, had only marginal influence on the amounts eluted in the leachates. Downward movement of tebufenozide from the top 2‐cm layer to the untreated middle and bottom layers (3‐cm segments) was consistently lower when the analytical material was used for fortification, than when the two formulations were used. Downward movement was higher for RH‐5992 2F than for RH‐5992 ES. Persistence of tebufenozide in substrates, maintained under submerged conditions for 70 days after leaching, indicated an initial 2‐week lag period prior to the onset of degradation. Formulation‐related differences were observed in the half‐life (DT₅₀) values. When the analytical material was used for fortification, the DT₅₀ ranged from ca 54 to 59 d. However, when the formulations were used for fortification, the DT₅₀ showed a higher range, i.e., from ca 62 to 67 d for RH‐5992 2F and ca 70 to 80 d for RH‐5992 ES. Formulation ingredients appear to have caused enhanced adsorption of tebufenozide onto the substrates, thus delaying degradation.     

Integrating soil carbon cycling with that of nitrogen and phosphorus in the watershed model SWAT: Theory and model testing

In this paper we describe and test a sub-model that integrates the cycling of carbon (C), nitrogen (N) and phosphorus (P) in the Soil Water Assessment Tool (SWAT) watershed model. The core of the sub-model is a multi-layer, one-pool soil organic carbon (S_C) algorithm, in which the decomposition rate of S_C and input rate to S_C (through decomposition and humification of residues) depend on the current size of S_C. The organic N and P fluxes are coupled to that of C and depend on the available mineral N and P, and the C:N and N:P ratios of the decomposing pools. Tillage explicitly affects the soil organic matter turnover rate through tool-specific coefficients. Unlike most models, the turnover of soil organic matter does not follow first order kinetics. Each soil layer has a specific maximum capacity to accumulate C or C saturation (S_x) that depends on texture and controls the turnover rate. It is shown in an analytical solution that S_x is a parameter with major influence in the model C dynamics. Testing with a 65-yr data set from the dryland wheat growing region in Oregon shows that the model adequately simulates the S_C dynamics in the topsoil (top 0.3 m) for three different treatments. Three key model parameters, the optimal decomposition and humification rates and a factor controlling the effect of soil moisture and temperature on the decomposition rate, showed low uncertainty as determined by generalized likelihood uncertainty estimation. Nonetheless, the parameter set that provided accurate simulations in the topsoil tended to overestimate S_C in the subsoil, suggesting that a mechanism that expresses at depth might not be represented in the current sub-model structure. The explicit integration of C, N, and P fluxes allows for a more cohesive simulation of nutrient cycling in the SWAT model. The sub-model has to be tested in forestland and rangeland in addition to agricultural land, and in diverse soils with extreme properties such high or low pH, an organic horizon, or volcanic soils.     

地质封存中CO_2盐水溶液的表观摩尔体积模型

在现有CO2盐水溶液密度模型的基础上,根据CO2地下盐水溶液密度实验数据,考虑了温度、压力和CO2质量分数三个参数的影响,建立了CO2盐水溶液的表观摩尔体积模型。模型结果表明该模型能在30~50℃、10~20 MPa温压范围内准确预测CO2在盐水溶液中的表观摩尔体积,将预测结果与实验数据进行对比发现最大相对误差为0.25%,平均相对误差为0.1%,模型预测精度明显高于现有的CO2盐水溶液表观摩尔体积模型,为CO2地下盐水层封存提供了必要的基础。