溶解性有机质对菲在沉积物上吸附与解吸性能的影响

采集了北京通州凉水河(标记为L)以及广东东江流域(标记为D)的沉积物,并进行菲(Phe)的连续吸附-解吸实验,研究了不同含量及组成的溶解性有机质(DOMs)对其吸附与解吸性能的影响.结果表明,DOMs能明显抑制菲在沉积物上的吸附,在实验浓度范围内(0~110mg/L),菲在沉积物上的吸附量与DOC浓度呈显著的负线性相关,并且DOC浓度越高,对吸附作用的抑制越显著.在溶解性有机质存在条件下,菲在2种沉积物上的吸附均呈线性吸附特征,kd值随加入沉积物浸出液DOC浓度的减小呈增大的趋势.菲在2种沉积物上的解吸过程均呈现一定的迟滞性,其解吸迟滞性可用热力学指数TII来描述.随着菲初始浓度的增加,TII值先减小后增加,其变化可以用吸附在高低位点上的菲分子比例以及菲分子是否能够被禁锢在吸附剂微孔内部来加以解释;溶解性有机质的存在,能促进菲从沉积物上的解吸,从而使菲的解吸滞后性减弱, 增强其在水环境介质中的迁移与传输能力.     

VARIATION OF DRAINAGE DENSITY IN A SMALL BRITISH COLUMBIA WATERSHED1

ABSTRACT: Short-term fluctuations in stream length were monitored in a small watershed located 10 kilometers east of Vancouver, British Columbia. Variation in discharge was reflected in a log-normal relationship with expansion and contraction of the stream net. The analysis of the variation of drainage density data using the individual hydrograph revealed a hysteresis effect. The stream net (as measured by drainage density) expanded more rapidly on the rising limb than it contracted on the recessional limb.     

菲在沉积物上的吸附-解吸研究

采用批量实验的方法,研究了盐度对菲在沉积物上的吸附的影响以及菲的初始浓度、沉积物结构性质改变、盐度对菲解吸的影响,并深入讨论了不可逆吸附的机制.结果表明,提高盐度促进菲的吸附,促进程度与沉积物所含有机质（SOM）有关.由菲吸附增加计算得到的盐常数0.299 L·mol^-1高于由菲溶解度降低计算得到的盐常数0.125 L·mol^-1.菲的解吸具有不同程度的迟滞性,实验数据用Freundlich方程拟合,解吸迟滞性用热力学指数TII表征.随着菲初始加入浓度增加,TII值先降低后又增加,以淡水中菲的解吸为例,随着菲初始浓度由0.5 mg·L^-1增加到2.5 mg·L^-1,TII值先由0.80降到0.38又增加到0.55,表明解吸迟滞性呈先下降后增加的趋势.氢氧化钠处理后的沉积物与原沉积物相比解吸迟滞性减弱,TII值由0.55降到0.33,说明对菲的锁定能力变弱.首次报道了盐度对菲解吸的迟滞性影响,结果表明,菲的解吸迟滞性指数TII值由淡水中的0.55减少到盐水中的0.42,说明盐水中菲解吸迟滞性比淡水中弱,解吸迟滞性的变化可以用菲分布到的吸附点位能量高低不同以及菲分子是否能够锁定在吸附剂内部微孔来解释.     

土壤-水体系中固/液比对溶解性石油烃吸附的影响

采用批实验的方法,研究了2种土壤在不同的固/液比（solid-to-solution ratio,SSR）条件下对溶解性石油烃（DPH）的吸附-解吸特性.结果表明,DPH在土壤中的吸附-解吸等温线符合线性方程;解吸表现出明显的滞后现象,滞后因子随SSR的升高而增加,随土壤有机碳含量（OC）的升高而减小,对于OC=1.54%的稻田土,当SSR从10.00 g·L^-1变化至75.00 g·L^-1,DPH的解吸滞后因子从1.43升高到2.21;对于OC=15.91%的黑土,当SSR从2.50 g·L^-1变化至5.00 g·L^-1,DPH的解吸滞后因子从1.18升高到1.37.说明吸附的不可逆性随SSR的升高而增强,随土壤有机碳含量的升高而减弱.另外,研究发现由吸附等温线计算得到的k_OC随SSR的升高（不可逆性的增强）而减小,在此基础上建立了固定体系中k_OC与SSR的关系模型,用于预测实际环境中DPH在土-水界面的迁移.     

Sorption-desorption behavior of polybrominated diphenyl ethers in soils

Polybrominated diphenyl ethers (PBDEs) are flame retardants that are commonly found in commercial and household products. These compounds are considered persistent organic pollutants. In this study, we used 4,4′-dibromodiphenyl ether (BDE-15) as a model compound to elucidate the sorption and desorption behavior of PBDEs in soils. The organic carbon-normalized sorption coefficient (K_OC) of BDE-15 was more than three times higher for humin than for bulk soils. However, pronounced desorption hysteresis was obtained mainly for bulk soils. For humin, increasing concentration of sorbed BDE-15 resulted in decreased desorption. Our data illustrate that BDE-15 and probably other PBDEs exhibit high sorption affinity to soils. Moreover, sorption is irreversible and thus PBDEs can potentially accumulate in the topsoil layer. We also suggest that although humin is probably a major sorbent for PBDEs in soils, other humic materials are also responsible for their sequestration.     

Effects of Land Use and Sample Location on Nitrate‐Stream Flow Hysteresis Descriptors during Storm Events

The U.S. Geological Survey's New Jersey and Iowa Water Science Centers deployed ultraviolet‐visible spectrophotometric sensors at water‐quality monitoring sites on the Passaic and Pompton Rivers at Two Bridges, New Jersey, on Toms River at Toms River, New Jersey, and on the North Raccoon River near Jefferson, Iowa to continuously measure in‐stream nitrate plus nitrite as nitrogen (NO₃ + NO₂) concentrations in conjunction with continuous stream flow measurements. Statistical analysis of NO₃ + NO₂ vs. stream discharge during storm events found statistically significant links between land use types and sampling site with the normalized area and rotational direction of NO₃ + NO₂‐stream discharge (N‐Q) hysteresis patterns. Statistically significant relations were also found between the normalized area of a hysteresis pattern and several flow parameters as well as the normalized area adjusted for rotational direction and minimum NO₃ + NO₂ concentrations. The mean normalized hysteresis area for forested land use was smaller than that of urban and agricultural land uses. The hysteresis rotational direction of the agricultural land use was opposite of that of the urban and undeveloped land uses. An r² of 0.81 for the relation between the minimum normalized NO₃ + NO₂ concentration during a storm vs. the normalized NO₃ + NO₂ concentration at peak flow suggested that dilution was the dominant process controlling NO₃ + NO₂ concentrations over the course of most storm events.     

长吉图开发开放先导区固定资产投资效益及其滞后效应分析

随着国家对长吉图先导区经济发展支持力度的加大,对其固定资产投资将会进入一个高速增长时期。因此,通过切实提高长吉图先导区域的固定资产投资效益,对化解长吉图先导区乃至整个吉林省潜在的资金风险,实现区域经济的可持续发展具有极其重要的意义。在分析长吉图先导区固定资产投资与经济增长相关性的基础上,通过建立区域固定资产投资效益模型,全面系统地研究长吉图先导区固定资产的投资效益,并进一步建立投资效益的一期滞后模型。研究结果表明,长吉图先导区的经济增长与固定资产投资额之间密切相关,且滞后一期固定资产投资对长吉图先导区GDP增量的滞后效应最为显著。在实证研究的基础上,提出解决问题的有效措施以及具体的政策建议。     

Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.     

Adsorption and desorption of herbicide monosulfuron-ester in Chinese soils

Monosulfuron-ester is a new, low rate, sulfonylurea herbicide that is being promoted for annual broadleaf and gramineal weed control; however, there is a lack of published information on its behavior in soils. The adsorption and desorption of monosulfuronester by seven type soils were measured using a batch equilibrium technique. The results showed that the Freundlich equation fitted its adsorption and desorption well, and the Freundlich constant values (Kf-ads) ranged from 0.88 to 5.66. Adsorption isotherms were nonlinear with 1/nf-ads values < 1. Soil pH, organic matter (OM), and clay content were the main factors influencing its adsorption and desorption. Adsorption and desorption were negatively correlated with pH 4.0–8.0 while positively correlated with OM and clay content. The adsorption of monosulfuron-ester was mainly a physical process, because its free energy (ΔG) in seven soils was less than 40 kJ/mol. Monosulfuron-ester adsorption by three soils increased with increasing CaCl2 concentration using CaCl2 as a background electrolyte. Monosulfuron-ester desorption was hysteretic in all tested soils.     

亚稳平衡态吸附(MEA)理论——传统吸附热力学理论面临的挑战与发展

传统吸附热力学是建立在吸附密度（吸附量，mol/m^2)为热力学状态函数的基础之上的。MEA理论指出，实际反应的吸附密度具有非状态函数的本质，在这个新的基础之上推导所得的MEA不等式指出；传统定义的吸附反应平衡常数具有热力学非常数性，它从根本上受反应过程（如可逆性，动力学）的影响，因此无法用来准确描述实际反应的平衡特征。只有建立可以描述亚稳平衡态吸附的理论体系，才有可能准确表征实际吸附反应的平衡限度，本文综述了MEA理论的宏观热力学原理以及应用该理论解决实际环境科学问题的3个范例。一是用MEA理论解释了国际上界面吸附领域中长期悬而未解的“固体浓度效应”问题，二是用MEA理论发现了环境生物地球化学中磷循环所遵循的一个基本原理和规律。三是用MEA原理改造地球化学与土壤化学中常用的固液分配系数（Kd)的定义（即重新定义Kd)。这3个范例分别代表了由MEA概念所引发的新的研究方向，最后介绍了从分子水平实验验证和发展MEA理论的最新结果以及用XAFS（X光精细结构吸收光谱）所发现的金属离子在水合金属氧化物表面上吸附的微观机制，这一发现可以统一解释金属离子在水合金属氧化物表面上静电吸附。离子交换吸附，非离子交换吸附，外层表面络合物，内层表面络合物，表面沉淀等作用力的本质以及这些作用之间的过渡与联系。