1,2-二氯乙烷和1,2-二氯丙烷在某污染场地包气带的吸附-解吸特性

1,2-二氯乙烷(1,2-DCA)和1,2-二氯丙烷(1,2-DCP)是某污染场地地下水中检出最高的挥发性有机污染物。文中采用批试验方法,研究污染场地包气带中三种不同深度土壤样品对1,2-DCA和1,2-DCP的吸附-解吸特性。结果表明:土壤中有机质决定其吸附行为,三种土壤对1,2-DCA和1,2-DCP的吸附符合Henry线性等温方程,分配系数在20.49～22.43L.kg-1,1,2-DCA和1,2-DCP在三种土壤中分别具有相似的吸附能力;同一土壤中两种目标污染物的吸附能力为Kd(1,2-DCA)>Kd(1,2-DCP),但差别不大。1,2-DCA和1,2-DCP在三种土壤中的解吸可用Freundlich等温方程拟合,解吸的难易程度与土壤中黏粒含量相关,黏粒含量越高,目标污染物的解吸越困难,第三层(地下4.9～5.1m)土壤的防污能力较强;两种污染物在三种土壤中的解吸都存在明显的滞后效应,1,2-DCP的滞后指数比1,2-DCA的大。     

秋季黄河pCO2控制因素及水-气界面通量

根据2006年11月1~10日,秋季黄河平水期二氧化碳分压(pCO₂)的现场实测数据及相关同步观测资料,对黄河表层水pCO₂的分布及其影响因素进行了研究。结果表明:水体pCO₂在80~166Pa,平均值110Pa,在世界主要河流中属中等偏下水平;空间分布存在较大的不均匀性,中游高于上游和下游。浮游植物的光合作用对pCO₂有一定的影响但强度较弱,即使在叶绿素最高值3.58μg/L的包头站pCO₂仍达到91Pa。黄河水体有机物含量较低且继承了陆源有机物难降解的特性,干流和库区EpCO₂/AOU的比值为0.14和0.20,远低于生物好氧呼吸作用控制水体pCO₂的理论下限0.62,因此,生物好氧呼吸作用对水体pCO₂的贡献不大。悬浮物(TSS)含量为3.77~1308mg/L,溶解无机碳(DIC)含量为3.03~4.14mmol/L,普遍高于世界其它河流且最大值均出现在潼关站;同时水体pCO₂与TSS、PIC、DIC含量具有极好的正相关性。因此黄河流域强烈的机械侵蚀和化学风化作用形成的碳酸盐体系是控制水体pCO₂的主要因素。利用Wanninkhof提出的淡水水-气交换系数的通量模式估算,黄河水域水-气界面CO₂交换速率约为0.229μmol/m2·s,秋季可向大气释放CO₂14.5亿moL,相当于8250km2草原或是112km2森林一年的固碳量。黄河CO₂释放通量与渥太华河相近,但要远小于亚马逊河。     

高盐强酸性地下水中复合苯系污染物原位芬顿氧化实验研究

在原位氧化过程中,实际场地地下水和含水介质的物化特征是影响氧化效果的重要因素,而目前对此影响的研究较少。以某场地实际高盐强酸性复合苯系污染地下水为研究对象,以地下水中2-硝基-4-甲氧基苯胺(2-nitro-4-methoxyaniline,2-N)和3-硝基-4-甲氧基苯胺(3-nitro-4-methoxyaniline,3-N)为特征污染物,探究芬顿(Fenton)试剂原位氧化特征,并研究液相环境因素(初始H2O2浓度、初始Fe2+浓度、初始pH值、初始醋酸(Acetic acid,HAc)浓度、初始SO4^2-浓度)以及含水层介质对Fenton法去除2-N和3-N的影响。结果显示:(1)Fenton法去除2-N和3-N效果显著,且在初始液相条件为c(H2O2)=7 mmol/L、c(Fe²⁺)=4 mmol/L、pH=4、c(HAc)=0 mg/L和c(SO4^2-)=0 mmol/L时去除效果最佳;(2)各因素对Fenton法氧化2-N和3-N的影响不同,加入H₂O₂和Fe²⁺使2-N和3-N去除率上升,增大HAc浓度使2-N和3-N去除率下降;(3)含水层介质对2-N和3-N具有一定吸附性,且对3-N的吸附性强于2-N,二者在本实验中最大吸附态占比分别为29%和42%,而吸附态的存在会抑制Fenton法对2-N和3-N的去除;(4)矿物分析结果显示介质含有少量黄铁矿,在硫酸环境下,介质腐蚀溶解释放Fe²⁺,在达到一定浓度后,无需额外添加Fe²⁺即可完成Fenton反应进而去除2-N和3-N。     

基于砂槽电化学-水动力学循环系统氯代烃反应迁移实验与模拟研究

在室内砂槽实验尺度,建立了潜水-微承压含水层中电化学-水动力循环系统下混合氯代烃生物降解的反应迁移模型,求取了混合氯代烃体系中各组分的反应动力学参数,并基于模型探究了含水层性质及工艺参数对该修复过程的影响机制.研究结果表明:（1）增大抽水流量可加快反应速率常数大的污染物降解,同时也会抑制反应速率常数较小的污染物去除.（2）增大电流强度和井内电极对氯代烃的好氧降解和厌氧脱氯过程分别具有促进和抑制作用.（3）含水层非均质性越强,氯代烃降解速率越小,这尤其体现在低渗区,且含水层非均质性对易降解污染物修复效果的影响较小.      

浅层地下水氯代烃污染天然衰减速率的估算

天然衰减恢复技术是恢复和控制浅层地下水氯代烃污染的技术之一,如何简便获取可靠的氯代烃衰减速率常数是该技术应用的一个关键。趋势线分析方法是一种简便有效的方法,在污染羽状体稳定的条件下,通过地下水流向上至少3口监测井的资料,能够比较准确地估算出污染物的天然衰减速率常数和生物降解速率常数。某氯代烃污染典型区的应用实例研究表明,该区四氯乙烯(PCE)的天然衰减速率常数和生物降解速率常数分别为0·000925d-1和0·000537d-1,证实该区浅层地下水中的PCE存在天然生物降解,但降解速率比较缓慢。忽略吸附作用的天然衰减容量计算所得出的天然衰减速率常数明显小于实际结果,说明尽管典型区包气带及含水层介质的有机碳含量很少,但它们对PCE的吸附作用不容忽视。     

吸附对土壤水环境中有机污染物生物降解过程的影响研究

在土壤水环境系统中,吸附作用是影响有机污染物生物降解过程的主要制约因素。污染物的吸附性越强,则其存在于土壤水溶液的重量百分比就越小,生物降解可能性也就越低。本文建立了定量描述吸附作用对有机污染物在土壤颗粒内部传输过程影响的数学模型。通过模型计算发现,有机污染物的土壤-水吸附分配系数Kd越大,则其从土壤颗粒内部传输到外部水溶液的速率就越小,总的降解速率也就越低。     

Effects of industrial by-product amendments on As,Cd and Tl retention/release in an element-spiked acidic soil

To asses the efficiency of two by-products (phosphogypsum (PG) and sugar foam (SF), rich in gypsum and calcium carbonate, respectively) in the immobilization of three toxic elements (As, Cd and Tl) in an acidic soil, batch-scale sorption and desorption experiments were conducted after 18 months of in situ amendment application. The Langmuir isotherms applied for sorption studies showed that the estimated maximum sorption capacity of the elements was highest in the SF-treated samples. The amount of element retained and the percentage of extraction after TCLP tests indicated that those samples amended with sugar foam (SF and PG + SF) had the potential to immobilize As, Cd and Tl in an acidic soil with low sorptive capacity. In addition to sorption and desorption experiments, scanning electron microscopy in back-scattered electron mode (SEM-BSE) showed the formation of Al-hydroxy polymers which provides the soil with additional sorption capacity. The three target elements were associated with the Al-hydroxy polymers, probably through direct coordination or the formation of ternary complexes. By means of statistical analysis it has been found that sorption processes of As, Cd and Tl in this soil mainly depend on the treatment, whereas desorption is an element-dependent process.     

Kinetics of neptunium(V) sorption and desorption on goethite: An experimental and modeling study

Various sorption phenomena, such as aging, hysteresis and irreversible sorption, can cause differences between contaminant (ad)sorption and desorption behavior and lead to apparent sorption ‘asymmetry’. We evaluate the relevance of these characteristics for neptunium(V) (Np(V)) sorption/desorption on goethite using a 34-day flow-cell experiment and kinetic modeling. Based on experimental results, the Np(V) desorption rate is much slower than the (ad)sorption rate, and appears to decrease over the course of the experiment. The best model fit with a minimum number of fitting parameters was achieved with a multi-reaction model including (1) an equilibrium Freundlich site (site 1), (2) a kinetically-controlled, consecutive, first-order site (site 2), and (3) a parameter ψ_2,de, which characterizes the desorption rate on site 2 based on a concept related to transition state theory (TST). This approach allows us to link differences in adsorption and desorption kinetics to changes in overall reaction pathways, without assuming different adsorption and desorption affinities (hysteresis) or irreversible sorption behavior a priori. Using modeling as a heuristic tool, we determined that aging processes are relevant. However, hysteresis and irreversible sorption behavior can be neglected within the time-frame (desorption over 32 days) and chemical solution conditions evaluated in the flow-cell experiment. In this system, desorption reactions are very slow, but they are not irreversible. Hence, our data do not justify an assumption of irreversible Np(V) sorption to goethite in transport models, which effectively limits the relevance of colloid-facilitated Np(V) transport to near-field environments. However, slow Np(V) desorption behavior may also lead to a continuous contaminant source term when metals are sorbed to bulk mineral phases. Additional long-term experiments are recommended to definitely rule out irreversible Np(V) sorption behavior at very low surface loadings and environmentally-relevant time-scales.     

Organic Contamination of Soil and Goundwater in the Piedimont Plain of the Taihang Mountains

The risk of groundwater contamination following the infiltration of waste surface water, is of great interest, particularly in areas experiencing water shortage. In this study, the distribution characteristics of contaminants along the Cihe River, in the piedimont plain of the Taihang Mountains, China, was investigated by measuring the soil and water samples. The main organic contaminants detected in different media include hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, and pesticides. The main contaminants found in different media are mostly derived from the river water, which can be seen from the results of waste water from the river and groundwater, from the soil samples from different depth and distance of the profiles along the river. The distribution characteristics showed that there has been a natural attenuation of the contaminants from the river during their transportation through the soils and groundwater. The sorption of organic compounds to soil organic matter is thought to be a main mechanism of natural attenuation.     

Experimental sorption of Ni, Cs and Ln onto a montmorillonite up to 150°C

The effect of temperature on the sorption of cations onto a dioctahedral smectite was investigated by running batch experiments at 25, 40, 80 and 150°C. We measured the distribution coefficient (Kd) of Cs⁺, Ni²⁺ and 14 lanthanides (Ln³⁺) between solutions and the montmorillonite fraction of the MX80 bentonite at various pH and ionic strengths. Up to 80°C we used a conventional experimental protocol derived from Coppin et al. (2002). At 150°C, the experiments were conducted in a PTFE reactor equipped with an internal filter allowing the sampling of clear aliquots of solution.The results show a weak but measurable influence of the temperature on the elements sorption. Kd’s for Ni²⁺ and Ln³⁺ increase by a factor 2 to 5 whereas temperature raises from 25 to 150°C. This effect seems higher at high ionic strength. The estimated apparent endothermic sorption enthalpies are 33 ± 10 kJ.mol⁻¹ and 39 ± 15 kJ.mol⁻¹ for Ni²⁺ and Eu³⁺, respectively. On the other hand, the temperature effect on Cs⁺ sorption is only evidenced at low ionic strength and under neutral conditions where the Kd decreases by a factor 3 between 25 and 150°C. Apparent exothermic sorption enthalpy for Cs⁺ on the montmorillonite is −19 ± 5 kJ.mol⁻¹.Experiments conducted at the four temperatures with the coexistence of all of the cations in the reacting solution (100 ppb of each element in the starting solution) or only one of them, produced similar values of Kd. This suggests the absence of competition between the sorbed cations, and consequently a low degree of saturation of the available sites. A fractionation of the lanthanides spectrum is also observed at high pH and high ionic strength whatever the temperature.The conclusion of this study is that the temperature dependence on sorption reflects, as the fractionation of REE or the pH and ionic strength effects, the chemical process which controls the overall reaction. In the case of an exchange dominated reaction (low pH and low ionic strength), the temperature effect is negligible. In the case of surface complexation (high pH and high ionic strength), the observed increase of Kd with temperature reflects either an increase of the sorption equilibrium constant with temperature or an endothermic property for reactions describing the montmorillonite surface chemistry.     

Volatile organic compounds in open ocean and coastal surface waters

Volatile organic compounds with volatilities ranging between those of n-hexane and n-pentadecane were identified in open ocean and coastal marine surface water samples taken in the north central part of the Gulf of Mexico. Approximately 40 organic compounds were found. The types and concentrations of the compounds found depended upon the extent of anthropogenic and terrestrial influences. Open ocean samples consisted mostly of aromatic hydrocarbons, whereas coastal samples included alkanes, cycloalkanes, cycloalkenes, aromatic hydrocarbons, aldehydes and chlorinated hydrocarbons. Unpolluted open ocean and coastal water samples had individual concentrations rarely exceeding 5 ng/kg; some aromatic hydrocarbons approached 15 ng/kg. n-Pentadecane dominated the hydrocarbons in these samples (50–100 ng/kg). The most polluted coastal water samples had individual volatile organic concentrations as great as 150 ng/kg with total concentrations approaching 1000 ng/kg. The terpene, limonene, was found extensively in the coastal samples (up to 40 ng/kg). Photooxidization of hydrocarbons in industrial/urban atmospheres was considered as a possible source of aldehydes present in coastal water. The dynamic headspace stripping/Tenax-GC adsorption method coupled with packed column gas chromatography, and gas chromatography-mass spectrometry were used for volatile organic analysis.     

红壤中矿物表面对腐殖质吸附萘的影响

矿物表面可改变土壤腐殖质对疏水性有机污染物的结合能力。采用红壤和高岭石分别与胡敏酸结合制备得到的两种复合体对萘的吸附等温线非线性显著,其n=0.76或0.74,并且有机碳归一化吸附分配系数的实验值Koacds是采用Kow计算得出的理论值Koc的5倍以上,表明红壤、高岭石均对腐殖质吸附萘有强化作用,且红壤较之高岭石对腐殖质吸附萘的影响稍强些。主要原因是,红壤中除了高岭石外,还有与腐殖质结合力很强的铁氧化物,而且很可能是吸附态腐殖质组成结构形态发生了有利于对萘吸附的改变。