水溶性有机质对土壤吸附芘的影响

多环芳烃(PAHs)有高疏水特性,再加上土壤对PAHs的吸附作用,使得PAHs污染土壤的生物修复十分困难。水溶性有机物(Dissolved Organic Matter,DOM)虽仅占土壤有机质的很小部分,却是影响PAHs在土壤中的转化、迁移的重要因子。为了认清DOM在生物修复PAHs污染土壤中的影响作用,以四环的芘作为目标污染物,以蚯蚓粪和生猪粪作为DOM的主要来源,研究了去除内源DOM土壤和原土壤吸附PAHs的区别,探索了不同用量、不同分子量、不同来源的DOM对土壤吸附芘的影响。结果表明,(1)内源DOM抑制土壤对芘的吸附作用,去除内源DOM可促进土壤对芘的吸附。(2)不同用量DOM对土壤吸附有机污染物的作用取决于DOM的临界值质量浓度、水土比及其吸附机理。当水土比为124,DOM小于临界值时,DOM对有机物增溶起主要作用,DOM的增加抑制芘的吸附;当DOM大于临界值时,共吸附和累积吸附起主要作用,DOM促进芘的吸附。当水土比为49时,DOM质量浓度的增大能促进芘的吸附。当水土比为24时,DOM质量浓度的增大抑制芘的吸附。(3)DOM的大分子量组分质量浓度越高,对芘的增溶作用越大,更能促进芘的溶解,从而抑制土壤对芘的吸附,小分子量组分DOM的作用则相反;中分子量DOM对土壤吸附芘的影响类似于大分子量DOM。研究DOM对土壤吸附芘的影响,对于PAHs污染土壤的修复有着重要的意义。     

地质吸附剂对萘的吸附与解吸行为研究

应用振荡平衡实验方法对萘在地质吸附剂上的吸附和解吸行为进行了研究,结果表明:萘在地质吸附剂上的吸附与解吸均呈现出明显的非线性和解吸滞后现象,这种吸附与解吸特性可能与地质吸附剂的内部结构之间存在一定的内在联系,结构的刚性、还原性和芳香性越大的地质吸附剂,对萘吸附和解吸的非线性愈强,解吸滞后愈明显.     

水体中悬浮颗粒物对酞酸酯的吸附和解吸特性

选择水体中的悬浮颗粒物(SPM)--沉积颗粒物和浮游植物颗粒(铜绿微囊藻和普通小球藻),研究它们对邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异辛酯(DEHP)的吸附和解吸行为.结果表明,SPM对DBP 和DEHP的吸附在很短的时间内即可达到平衡,沉积颗粒物约为2h,浮游植物颗粒约为0.5h;SPM对DEHP的吸附能力明显大于DBP;不同SPM对同一种化合物的吸附能力差异较大,这与颗粒物中有机质的类型和结构有关;在实验浓度范围内,SPM对DBP和DEHP的吸附和解吸等温线具有较好的线性关系,解吸过程存在明显的迟滞现象,且沉积颗粒物比浮游植物颗粒物具有明显的迟滞效应,DBP比DEHP具有较大程度的迟滞效应.     

疏水性有机污染物在草甸土中的吸附和解吸行为

研究5种有机污染物在草甸土中的吸附和解吸行为.结果表明,污染物在土壤中的吸附主要受疏水性作用的影响,吸附数据基本符合传统的线性模型.解吸行为则表现出明显的滞后现象,解吸实验结果与"双元平衡解吸(DED)模型"的预测值相吻合.DED模型能够更加准确地定量描述疏水性有机污染物的解吸行为.     

磷对褐土中锌镉次级吸附和解吸影响

通过吸附和解吸试验,研究了不同磷吸附量石灰性褐土对锌镉次级吸附和解吸的影响。结果表明,次级吸附锌和镉对不同吸附量磷土壤的磷解吸量随磷吸附量的增加而增加,而磷解吸量随次级吸附后锌、镉浓度的增加而降低,即随锌镉添加量的增加,磷的有效性有所降低。土壤对锌的次级吸附量和吸附率随磷吸附量的增加先降低后升高,并随添加镉浓度的增加而降低,解吸量和解吸率随磷吸附量的增加而增加,说明在正常施磷范围内,增加磷的施用量能提高土壤中锌的有效性,同时,土壤对高浓度锌的次级吸附率小于低浓度锌的次级吸附率,而土壤对高浓度锌的解吸量和解吸率要远大于对浓度锌的解吸量和解吸率;土壤对镉的次级吸附量、吸附率和解吸量、解吸率都随着磷吸附量的增加而增加,且吸附量随添加镉的量增加而增加,但镉次级吸附量和吸附率随添加锌浓度的增加而减小,解吸量和解吸率却增大,说明在磷吸附量相同的条件下,添加锌促进了镉的有效性。     

水溶性有机质对土壤吸附有机污染物的影响

在自然环境中,水溶性有机质(DOM)会对土壤吸附有机污染物产生影响.基于已有的成果,本文综合分析了DOM的有关因素对土壤吸附有机污染物的影响.研究表明,不同来源的DOM的亲疏水组分比例不同;随着腐解时间的增长,亲水组分减小,疏水组分增加.外源DOM的极性与亲疏水组分所含官能团的种类和数量、分子量均会影响有机污染物的吸附;DOM的临界值浓度与土壤有机质含量负相关.当DOM浓度大于临界值时抑制吸附,反之促进吸附.DOM具有酸碱缓冲作用,影响土壤溶液的pH,进而影响对有机污染物的吸附.由于土壤内源DOM对有机污染物具有增溶作用,会抑制土壤吸附有机污染物.论文最后对今后的相关研究方向提出了建议.     

污染土壤中苯系物的热解吸

以苯系物(BTEX)污染土壤为对象,研究温度和加热时间对土壤中污染物BTEX解吸的影响,初步探讨BTEX各污染物沸点与分子量大小和去除效率的关系.结果表明,随温度的提高,污染物BTEX的饱和蒸汽压也会随之增大,导致其在土壤中挥发性增强;采用一阶衰减模型计算BTEX热解吸的衰减常数,得出温度和加热时间可直接影响解吸过程;同时通过对BTEX各污染物去除率的比较,表明分子量越大,沸点越高的污染物,越不易被解吸出.通过加热可增强土壤中BTEX的热解吸,对热解吸现场小试的开展奠定了基础.     

Fenton氧化处理对土壤中芘的生物可利用性的影响

研究发现蚯蚓吸收土壤中污染物芘的速率很快,10 d后蚯蚓体内富集污染物浓度基本达到稳定态;土壤中的有机质是影响污染物迁移的重要因素,土壤有机质的含量越高对芘滞留(吸附)能力越强,蚯蚓富集芘的量越低,蚯蚓富集到体内污染物的浓度越低.这也说明土壤对污染物的吸附/解吸行为决定了土壤中污染物的生态风险;氧化处理降低了土壤中的有机质含量,改变土壤有机质的组成,氧化处理也降低了土壤中被吸附污染物芘对蚯蚓的生物有效性.     

表面活性剂及DOM对土壤中菲、芘解吸行为的影响因子初探

采用室内序批试验研究了土—水体系中非离子型表面活性剂(Tween80)和水溶性有机物(DOM)的投加次序、试验平衡时间及离子强度等环境因素对表面活性剂Tween80及DOM对污染土壤中菲、芘解吸行为的联合效应。结果表明,表面活性剂Tween80和DOM都可促进菲、芘的解吸,当两者同时加入体系时,菲、芘的解吸率是对照的2.55～3.12倍(菲)和7.61～9.61倍(芘),两者之间存在协同效应;与两者同时加入相比,振荡12h后加入Tween80,菲、芘的解吸率增加了1.81～3.3%(菲)和7.55～9.51%(芘),而振荡12h后加入DOM,菲、芘的解吸率基本无变化;试验还证实,随着离子强度的增加,体系中菲、芘解吸率呈下降趋势,但不同处理间无明显的差异性。     

硝磺草酮在黑土和红壤中的吸附-解吸特性

采用批量平衡实验,研究了硝磺草酮在黑土和红壤中吸附-解吸行为.结果表明,硝磺草酮在两种土壤中的吸附分为快速线性分配和慢速吸附两个阶段,2 h后,基本达到动态平衡.然而,其吸附速率随时间的延长而降低,且初始浓度和土壤性质对硝磺草酮吸附速率的变化率没有明显影响.硝磺草酮在红壤和黑土中吸附和解吸过程均能用Freundlich模型进行很好的拟合,拟合系数R2分别为0.999和0.993(黑土)、0.991和0.962(红壤).硝磺草酮在土壤中的吸附等温线呈现"L"型,以物理性吸附为主.硝磺草酮在两种土壤上的解吸过程存在一定的滞后现象,且随着硝磺草酮初始浓度增加,其解吸等温线的滞后系数也随之降低.黑土中硝磺草酮的吸附和解吸滞后强度均大于红壤.     

可溶性有机物对土壤中主要有机污染物环境行为的影响

概括了环境中可溶性有机物的特点，并系统总结了当前国内外关于可溶性有机物对土壤中主要污染物环境行为的影响的研究进展。阐述了可溶性有机物对农药、多环芳烃在土壤中的吸附、解吸及分配等环境行为所起的作用。最后指出了该方面研究存在的问题及今后应加强的方向。     

Effect of low molecular weight organic acids on adsorption and desorption of fluoride on variable charge soils

The effect of four low molecular weight organic acids on F⁻ adsorption by two variable charge soils was investigated using a batch method. The organic acids reduced F⁻ adsorption through competition by the acids with F⁻ for sorption sites. Oxalic and malonic acids, both of which have simpler chemical structures, were more effective than citric or malic acid. The effect of organic acids on F⁻ adsorption was more prominent at higher pH values and with larger amounts of the organic acids. The desorption study showed that the organic acids enhanced the desorption of F⁻ adsorbed by the soils. In the control and malic acid systems, desorption increased sharply with decreasing pH, while in the oxalic acid system, desorption rose slightly with decreasing pH. Desorption also increased with increasing amount of organic acid added. There are two possible mechanisms for the effect of the organic acids on F⁻ adsorption and desorption: (1)␣competition of the organic acids with F⁻ for adsorption sites and (2) dissolution of the adsorbents, especially dissolution of soil Al.     

风沙土不同有机组分对氨氮的解吸特征影响

采用平衡解吸法研究了风沙土不同有机组分对氨氮的解吸特征影响。结果表明,去除腐殖质后的风沙土氨氮解吸比例增加（由0.58增加到0.68）,同时,解吸迟滞性指数显著降低（由0.067降低到0.021）,说明腐殖质是影响风沙土氨氮解吸特征的重要因素;氨氮在轻组有机组分上的表面分配作用吸附是导致解吸比例增大,解吸迟滞性指数减小的原因;重组有机组分中的紧结态腐殖质（胡敏素）对氨氮的解吸起关键作用,它不但解吸比例较低（Dr=0.23）,而且解吸迟滞性指数较大（TⅡ=0.458）;氨氮在紧结态和稳结态腐殖质所形成的团聚体颗粒微孔隙中的不可逆吸附是导致解吸比例降低、解吸迟滞性指数增大的根本原因;考查土壤对氨氮的解吸特征不但要考虑有机质的含量,更要考虑有机质的存在形态,它也是影响土壤氨氮解吸特征的重要因素,轻组有机组分、重组有机组分及重组有机组分中的稳结态加紧结态腐殖质（HⅡ＋HⅢ组）和紧结态腐殖质（HⅢ组）携载的吸附态氨氮进入水体后,对上覆水体的扩散通量可分别按其饱和吸附量的0.94、0.58、0.33和0.23倍估算。     

Effects of dissolved organic matter on the desorption of Cd in freeze–thaw treated Cd-contaminated soils

Lab-scale experiments were conducted to investigate the effects of dissolved organic matter (DOM) on the desorption of Cd in freeze–thaw treated Cd-contaminated soils. The results indicated that DOM significantly facilitated the desorption of Cd from freeze–thaw treated soils when comparing with that of non-frozen soils. Effects of DOM on the Cd desorption were highly dependent on the soil type and contamination concentration. The maximum desorption ratios of Cd by DOM generated from straw and sludge were 15.6% and 13.65%, respectively, in brown soils, and the maximum desorption ratios reached 14.7% and 9.3%, respectively, when using black soils through the same treatment. The higher the Cd contamination concentration in soils, the higher the ratio of Cd desorption by DOM. This was because of the integrated effects of the soil properties changed by the freeze–thaw treatment and the species transformation of Cd. The characteristics of DOM, such as its concentration and properties, had shown obvious impacts on the Cd desorption by DOM. The desorption was promoted with the increased DOM concentration and the hydrophilic fraction, and lowered pH and the low-molecular-weight of DOM.     

草炭溶解态有机物质与Cu2+、Cd2+络合稳定性的研究

研究了由草炭提取的胡敏酸(HA)、富里酸(FA)、水溶解态有机物质(WSOM)的基团特征,分子量分布及其与Cu2+、Cd2+两种金属离子之间的络合稳定性。对HA、FA及WSOM的红外光谱研究显示三者的官能团组成相似,只是含量略有不同。固态13C-NMR对HA、FA及WSOM结构特征的描述以及水相凝胶色谱法对三种有机质样品的分子量及分子量分布的测定结果显示HA分子最大且含有大量的长链烷烃,而FA分子小得多,结构以碳水化合物及多糖为主,WSOM的分子量略低于FA,结构与FA相近。离子交换平衡法对三种有机质样品与Cu2+、Cd2+的络合配位数和稳定常数的测定结果显示两种介质条件下络合配位数(x)、络合稳定常数(logk)的次序均为:Cu2+>Cd2+;同一介质条件下,对不同有机质而言均满足:M-HA>M-FA>M-WSOM。     

Characterization of interaction between different adsorbents and copper by simulation experiments using sediment-extracted organic matter from Taihu Lake,China

The complex capacity of different types of organic matters （OMs） for Cu was quantitatively studied by simulation experiments using different adsorbents prepared from the sediment in Taihu Lake. The free Cu was measured with ion selective electrode （ISE） and complex capacity was calculated using a conditional formation constant model. The result indicated that the complex capacity was 0.048 mmol·g-1, 0.009 and 0.005 mmol.g-1for raw sediment, sediment without DOM, sediment without insoluble organic matters but with DOM and sediment without OM. Insoluble organic matter played a major role in the sorption of Cu in sediment and it can adsorb most Cu from water column. In the solution, Cu mainly existed as a complex with DOM and the DOM-Cu complexation capacity was 327.87 mg. g-1. The change of TOC and pH indicated ion-exchange in the interaction between free Cu and DOM. When the Cu concentration in the experiment reached the complex capacity of DOM, precipitation was the major mechanism to remove Cu from water phase, which was observed from UV absorbance change of DOM, that is, its aromaticity increased while molecular weight decreased. The desorption result indi- cated that DOM was more capable of desorbing Cu from adsorbents without OM than adsorbent with OM. The desorbed quantity with DOM was 1.65, 1.78 and 2.25 times higher than that with water for adsorbents without OM, raw adsorbents （sediment） and adsorbents without DOM.     

Effects of organic acids on Cd adsorption and desorption by two anthropic soils

The objective of this experiment was to study the effects of malic, tartaric, oxalic, and citric acid on the adsorption and desorption characteristics of Cd by two typical anthropic soils (lou soil and irrigation-silted soil) in North-west China. Cadmium adsorption and desorption were studied under a range of temperatures (25°C, 30°C, 35°C, 40°C), organic acid concentrations (0.5–5.0 mmol·L^-1), and pH values (2–8). The results showed that the Cd adsorption capacity of the lou soil was significantly greater than that of the irrigation-silted soil. Generally, Cd adsorption increased as the temperature increased. In the presence of NaNO₃, the adsorption of Cd was endothermic with ΔH values of 31.365 kJ·mol^-1 for lou soil and 28.278?kJ·mol^-1 for irrigation-silted soil. The endothermic reaction indicated that H bonds were the main driving force for Cd adsorption in both soils. However, different concentrations of organic acids showed various influences on the two soils. In the presence of citric acid, chemical adsorption and van der Waals interactions were the main driving forces for Cd adsorption rather than H bonds. Although the types of organic acids and soil properties were different, the effects of the organic acids on the adsorption and desorption of Cd were similar in the two soils. The adsorption percentage of Cd generally decreased as organic acid concentrations increased. In contrast, the adsorption percentage increased as the pH of the initial solution increased. The exception was that adsorption percentage of Cd increased slightly as oxalic acid concentrations increased. In contrast, the desorption percentage of Cd increased with increasing concentrations of organic acids but decreased as the initial solution pH increased.     

沙土不同有机组分对磷的解吸特征影响

采用平衡解吸法研究了沙土不同有机组分对磷的解吸附特征影响。结果表明,通过过氧化氢去除有机质后的沙土使磷的解吸比例（Dr=0.94）大幅度增加,解吸迟滞性指数（TⅡ=0.05）显著降低;有机质是影响磷在沙土上解吸特征的重要因素;磷在橡胶态胶体（轻组有机组分）上的表面分配作用吸附是导致解吸比例（Dr=0.81）增大,解吸迟滞性指数（TⅡ=0.05）减小的原因;稳结态腐殖质中的胡敏酸在对磷的吸着和滞留过程中发挥重要作用,HⅡ＋HⅢ组（Dr=0.57、TⅡ=0.30）;磷在紧结态腐殖质所形成的团聚体结构中引起的团聚体结构不可逆形变是导致磷的解吸比例（HⅢ组Dr=0.24）降低,解吸迟滞性指数（HⅢ组TⅡ=0.49）增大的根本原因,考查土壤磷的解吸特征不但要考虑有机质的含量,更要考虑有机质的存在形态,它也是影响土壤磷解吸特征的重要因素,轻组有机组分、重组有机组分、以及重组有机组分中的稳结态腐殖质、紧结态腐殖质所携载的吸附态磷进入水体后对上覆水体的释放通量可分别按其饱和吸附量的81%、66%、57%和24%进行估算。     

淹水还原作用下土壤镉的吸附与解吸特征的初步探讨

利用黄棕壤发育的水稻土(pH6.53),设置6个不同处理恒温(25±0.1)℃培养20d,初步探讨了3种还原强度土壤对Cd的吸附和解吸特征。试验数据显示:强度还原土壤,Eh和pH降低并稳定在-474mV和5.02水平,Cd吸附率由开始时的99.96%下降到94.70%,Cd解吸率平均为90.01%;中度还原土壤,Eh下降至-90mV左右,pH略有上升,Cd吸附率和解吸率平均分别为99.96%和66.09%;氧化态土壤的Eh、pH和Cd解吸率变化都比较小,平均分别为400.4mV、6.11和46.78%。此结果表明,处于不同还原状况下的土壤表面对Cd吸附和解吸有所差别;强度还原土壤对外源Cd的吸附率小于中度还原土壤对外源Cd的吸附率;土壤吸附外源Cd的解吸率,由大到小的次序依次为强度还原土壤,中度还原土壤,氧化状态土壤;还原程度越强,土壤对Cd的吸附率越低,Cd的解吸率也越高;还原条件下土壤Eh、pH、交换性亚铁和水溶性有机质含量是影响土壤Cd吸附和解吸的主要因素。     

Contribution of black carbon to nonlinearity of sorption and desorption of acetochlor on sediment

In order to investigate the contribution of various black carbon (BC) contents to nonlinearity of sorption and desorption isotherms for acetochlor on sediment, equilibrium sorption and desorption isotherms were determined to measure sorption and desorption of acetochlor in sediment amended with various amounts of BC. In this paper, two types of BC referred to as BC400 and BC500 were prepared at 400°C and 500°C, respectively. Higher preparation temperature facilitated the formation of micropores on BC to enhance its sorption capacity. Increase of the BC content obviously increased the sorption amount and reduced the desorption amount for acetochlor. When the BC500 contents in total organic carbon (TOC) increased from 0 to 60%, Freundlich sorption coefficient (K _f) increased from 4.07 to 35.74, and desorption hysteresis became gradually obvious.When the content of BC in TOC was lower than 23%, the sorption isotherm had a significant linear correlation (p = 50.05). In case of desorption, a significant nonlinear change could be observed when the content of BC was up to 13%. Increase of BC content in the sediment would result in shifting the sorption-desorption isotherms from linearity to nonlinearity, which indicated that contribution of BC to nonlinear adsorption fraction became gradually remarkable.