Characteristics of the natural organic matter sorption affects of organic contaminants

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Characteristics of natural organic matter affect sorption of organic contaminants

Several soil samples were used to study how the characteristics of natural organic matter (NOM) affect sorption of organic compounds. These soils contains different amounts and types of NOM. Aromaticity of NOM (percentage of aromatic carbons) was determined from solid-state CPMAS 13C NMR spectra and the soil effective polarity was computed from the equation developed by Xing et al. Naphthalene was used to examine the sorption characteristics of NOM. Both aromaticity and polarity of NOM strongly affected sorption of naphthalene. Old NOM showed higher affinity than that in the surface, young soils. Sorption increased with increasing aromaticity and decreasing polarity. Thus, the sorption coefficients of organic contaminants cannot be accurately predicted without some consideration of NOM characteristics.     

土壤不同有机质组分对菲的吸附特征研究

采用批次实验,研究了三种不同类型土壤黄红壤、水稻土和草甸土的全土、重组、去松结态和紧结态4个组分对菲的吸附,结果表明,菲在不同土壤及其组分上的吸附等温线都能用Freundlich方程进行拟合,所有等温线都具有一定程度的非线性,指数N值的大小顺序基本都为全土>重组>去松结态>紧结态.除了黄红壤的紧结态比去松结态对菲的吸附容量KF值略小外,不同土壤及其组分对菲吸附的KF值以及有机碳归一化的KFoc值大小顺序都为紧结态>去松结态>重组>全土.不同类型土壤之间的KF值大小顺序为草甸土>水稻土>黄红壤,而KFoc值大小顺为水稻土>草甸土>黄红壤.KF值与有机碳含量之间呈显著性正相关(P<0.05),KFoc与N之间呈极显著负相关(P<0.001).土壤及其组分对菲的吸附强度与有机质的结构特征和聚合程度有关.     

Sorption of dissolved organic matter and its effects on the atrazine sorption on soils

IntroductionApplication of organic amendments, such as sewagesludge to agricultural soils, has been considered as aneffective way to improve the soil physico chemical propertiesand organic matter compositions. Dissolved organic matter(D…     

Effects of dissolved organic matter from sewage sludge on sorption of tetrabromobisphenol A by soils

Sorption of tetrabromobisphenol A (TBBPA) by soil influences its fate and transport in the environment. The presence of dissolved organic matter (DOM) may complicate the sorption process in soil. The effects of DOM from sewage sludge on TBBPA sorption by three soils were investigated using batch equilibration experiments in the study. DOM was observed to be sorbed on the soils and the isotherms could be fitted by the Langmuir model. The effects of DOM on TBBPA sorption were dependent on the characteristics ...     

土壤胡敏酸对菲的吸附特征研究

通过模拟实验研究了不同来源的7种土壤样品及从中提取的胡敏酸(HA)对菲的吸附特征,应用元素分析仪和固相核磁共振光谱(CP／MAS^13C-NMR)对7种土壤样品中的胡敏酸进行了表征并计算其芳香度和脂化度．实验结果表明,不同来源土壤对菲吸附的Freundllich吸附系数(Kt)不同,其有机碳标化的分配系数(K IM)也存在一定的差异．另外,由于不同来源土壤中HA的结构和组成差异明显,土壤HA对疏水性有机污染物的吸附规律也表现出不同的特征．土壤中HA对菲吸附过程的有机碳标化的分配系数(K oc)与土壤HA的芳香度具有正相关性．     

Impacts of soil organic matter, pH and exogenous copper on sorption behavior of norfloxacin in three soils

Norfloxacin (Nor) sorption and the factors (soil organic matter (SOM), pH, and exogenous copper (Cu) influencing the sorption were investigated in a black soil (soil B), a fluvo-aquic soil (soil F), and a red soil (soil R). With increasing of Nor concentrations, sorption amount of norfloxacin increased in both the bulk soils and their SOM-removed soils, but the sorption capacity in SOM-removed soils was higher than that of their corresponding bulk soils, indicating that the process of norfloxacin sorption in soil was influenced by the soil properties including SOM. The sorption data in all bulk soils and SOM-removed soils were fitted to Freundlich and Langmuir models. The correlation coefficients suggested that the experimental data fitted better to Freundlich equation than to Langmuir equation. Furthermore, the data from soil F and SOM-removed F could not be described by Langmuir equation. The norfloxacin sorption amount decreased in soil B and soil F, whereas it increased in soil R as solution pH increased. The maximum KD and KOC were achieved in soil R when the equilibrium solution pH was 6. And the norfloxacin sorption was also influenced by the exogenous Cu2+ ions, which depended on the soil types and Cu2+ concentrations. With increasing of Cu2+ concentrations in solution, generally, sorption amount, KD and KOC for norfloxacin in soils increased and were up to a peak at 100 mg/L Cu2+, and then the sorption amount decreased regardless of norfloxacin levels.     

腐殖酸极性与有机农药吸附行为的关系

用不同的方法对腐殖酸(HA)进行了结构改性处理,并用元素分析仪、红外光谱仪和电位滴定仪对改性前后的HA进行了表征;通过振荡平衡法,研究了HA改性前后对有机农药甲基对硫磷、西维因、克百威的吸附行为.结果表明,水解处理使得HA的碳水化合物结构减少,肟化处理使得HA的C=N结构增加,氧化处理使HA的芳香环发生开环反应、-COOH基团增加,肟化和氧化处理均使得HA极性增强;有机农药甲基对硫磷、西维因、克百威通过分配作用吸附于HA,分配系数Kd与HA有的机碳含量成正比,HA的极性越强,吸附量越小.     

长期不同水分调控对污染场地土壤溶解性有机质含量及其结构特征的影响

为了考察不同水分调控下污染场地中土壤有机质和溶解性有机质（DOM）的演变过程,以2种冶炼厂重金属污染土壤为研究对象,通过恒温恒湿培养实验观察不同水分调控下土壤有机质和DOM的含量变化,并采用紫外-可见光谱和荧光光谱分析了土壤DOM的光谱特征.结果表明,水分调控180 d后,2种重金属污染土壤中有机质和DOM含量呈不同程度降低趋势,且随着水分含量增加,其降幅明显增加,最大降幅分别为33.28%和89.35%.水分调控过程中,土壤DOM中类蛋白物质最易发生降解,导致类富里酸和类腐殖酸的占比相应提高;随着水分含量增加,土壤DOM的芳香性提高,腐殖化程度升高,分子聚合度和分子量增大,最终导致DOM稳定性增强,上述结果有助于揭示水分诱导过程中DOM的变化对污染场地中重金属环境行为的影响.     

农田灰钙土中有机质和碳酸钙对Zn吸附-解吸行为的影响

采用序批平衡法,研究了Zn在去除有机质及去除碳酸钙前后灰钙土的吸附-解吸行为.结果表明,在试验土壤中吸附量均随着加入Zn浓度的增加而增加,且去碳酸钙土对Zn吸附固定能力明显低于灰钙土,即有机质对灰钙土Zn的吸附影响小于碳酸钙;去有机质及去碳酸钙前后灰钙土对Zn的吸附过程不适合用 Langmuir方程描述,而 Freundlich方程能够很好地拟合,调整后的决定系数R2￠均大于0.90,达到极显著水平(P<0.01);去除有机质和碳酸钙后灰钙土对Zn的解吸率都升高,且灰钙土去碳酸钙后解吸率略高于去有机质;去除有机质及碳酸钙前后灰钙土的解吸量均随吸附量的升高而升高,且去碳酸钙土解吸量最大,去有机质土次之,灰钙土最小;土壤有机质和碳酸钙对Zn均有较强的络合吸附效应,能有效降低Zn的迁移活性,从而促进吸附,抑制解吸.     

滇池泥炭土对两种抗生素和双酚A的吸附

用不同浓度NaOH溶液处理采集自云南滇池的泥炭土,研究处理前后的泥炭土对两种抗生素磺胺甲恶唑（SMX）、卡马西平（CBZ）及双酚A（BPA）的吸附机理,并深入探讨3种污染物及泥炭土性质对吸附特性的影响.吸附等温线拟合结果表明,Freundlich模型对3种物质在泥炭土上的吸附等温线有较好的拟合优度.3种物质中,BPA的非线性指数n值最低,这可能是由于其不对称的结构特征导致.随着处理泥炭土的NaOH浓度增加,3种吸附质在泥炭土上的吸附顺序为BPA > CBZ > SMX,BPA的吸附最高可能是由于其含有两个酚羟基,与泥炭土有较强的极性作用导致,而CBZ的吸附比SMX的吸附高是由憎水性作用引起.NaOH处理后并没有增加泥炭土对这3种吸附质的吸附,说明对于离子型化合物,吸附过程和机理复杂,BPA蝴蝶状结构及苯环上含有两个羟基可能导致其在泥炭土上出现特异性吸附,这导致其吸附系数最高;NaOH处理后泥炭土的有机碳含量增加但比表面积可能降低,从而使3种污染物的吸附降低.因此,本研究3种离子型化合物在泥炭土上的吸附受到吸附质的官能团及溶解度、泥炭土的有机碳含量及官能团等多种因素的影响.     

重金属污染的长春水田黑土对菲的吸附作用

以菲为多环芳烃(PAHs)代表物,研究了Pb、Zn、Cu污染后黑土对PAHs的吸附作用.结果表明,分配作用是黑土吸附菲的主要机制,无论重金属污染与否,黑土对菲的等温吸附曲线均呈线性.实验条件下,重金属污染后黑土对菲的吸附作用明显增强,且随重金属含量提高,黑土对菲的吸附系数(Kd)和有机碳标化的吸附系数(Koc)增大.由于重金属的“键桥”作用,黑土吸附菲的平衡溶液中水溶性有机质(DOM)浓度降低,土壤固相有机质含量略有增加(不超过原有有机质含量的0.53%).计算了这部分增加的固相有机质对菲的吸附系数K_Ph/soc,并分析了溶液中DOM对土壤吸附菲的影响.结果显示,溶液中DOM浓度变化及其与菲的结合作用对重金属影响土壤吸附菲的贡献甚微;而K_Ph/soc值则比土壤原有有机质对菲的吸附系数K_d值大2～3个数量级,这是重金属污染导致土壤吸附作用增强的根本原因.     

溶解性有机质对铁铝土吸附2,4-D的影响

以动力学吸附和等温吸附实验研究了2,4-D在铁铝土中的吸附特征,并比较了不同亲/疏水性溶解性有机质（DOM）对此的影响.结果表明：2,4-D在铁铝土中的动力学吸附符合伪一级动力学方程,等温吸附符合Henry,Freundlich方程,是一个物理作用主导的,自发的,放热的非均质吸附过程.吸附系数K_d为0.61~2.02L/kg,是一种难吸附有机污染物,对地下水存在环境风险.吸附量受土壤pH值影响显著,与土壤中矿物含量,粘粒组成等也密切相关.DOM共存条件下,高疏水性DOM,中疏水性DOM抑制了2,4-D在铁铝土的吸附,使K_d值下降10.7%~58.8%.低疏水性DOM对铁铝土吸附2,4-D作用不明显.DOM对铁铝土吸附2,4-D的作用效应与土壤理化性质和DOM性质密切相关.土壤矿物组分越多,粘粒含量越高,堵孔效应越大.DOM疏水性越大,对2,4-D吸附作用的增溶作用,堵孔作用也越大,其中HOA,HON是关键组分.     

天然有机物在氧化铝表面的吸附机理研究

考察了天然有机物(NOM)的2种分离组份(憎水部分HyO,亲水部分HyI)和一种商用腐殖酸(CHA)在氧化铝表面的吸附-解吸行为规律,从芳香性、分子量、极性的角度探讨了NOM自身特性对吸附性能的影响,并通过改变溶液性质(pH值、离子强度、二价阳离子Ca2 ),进一步论证了NOM在金属氧化物表面的吸附机理.结果表明,芳香性高、弱极性的有机物吸附性能较强;降低溶液的pH值,有助于增加吸附剂的吸附容量;离子强度和Ca2 对吸附行为的影响,与NOM自身和内部组分的性质有关.NOM吸附于金属氧化物表面的机理,可以归结为配位体交换、静电作用、憎水作用、阳离子架桥等多个因素共同作用的结果.采用原子力显微成像技术,进一步从微观角度证实了憎水作用和阳离子架桥作用的存在.     

Sorption of a triazol derivative by soils: importance of surface acidity

The sorption of a triazol derivative,1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)penten-3-ol with a common name of s3307D,on fifteen soils and three H2O2-treated soils was investigated.The sorption isotherm for each untreated and treated soil was nonlinear,and was best fitted to Freundlich sorption equation.Soils containing hith amount of clay content or organic matter or both sorbed much higher amounts of the chemical than soils that had low contents of these soil constituents.H2O2-treated soils showed sonsiderable sorptive affinity for S3307D.It was concluded that both organic matter and mineral fraction in natural soils contributed to the sorption of the basic compound.Sorption by the H2O2 treated soils increased as suspension pH decreased,but all suspension pHs exceeded the pKa of the compound by more than two units.This implies that organic base protonation can occur on surfaces of soil components,and surface acidity (exchangeable acidity)is important in sorption process of the organic base rather than suspension pH.     

源自腐殖土的溶解性有机质组分对棕壤和黑土吸附苯并三唑的影响

溶解性有机质(DOM)影响着有机污染物在土壤中的吸附行为.将从腐殖土中提取的DOM(DOMbulk)用XAD-8树脂和阴/阳离子交换树脂进行分级,用红外光谱、元素分析、紫外分光光度计和电位滴定的方法对DOM不同组分特征进行分析.用吸附批次实验方法研究了DOM不同组分对棕壤和黑土吸附苯并三唑(BTA)的影响.结果表明,DOMbulk中疏水酸性(HOA)、疏水中性(HON)、亲水酸性(HIA)、亲水碱性(HIB)和亲水中性(HIN)组分比例分别为61%、17%、6%、2%和14%.由于黑土有机碳(OC)含量高于棕壤,黑土对BTA和DOM组分的吸附能力均大于棕壤.相对于黑土,棕壤吸附DOM的标化分配系数Koc较高,其原因是棕壤中含有较多的对吸附DOM起重要作用的黏粒和粉砂.由于水分子占据DOM结合点位,DOM组分与BTA在溶液中结合较弱.DOMbulk中HIN在土壤上吸附最强.HIN的吸附增加了土壤吸附BTA的点位,增加点位的促进吸附作用大于HIN与BTA的竞争吸附作用,最终表现为促进吸附.疏水组分在土壤上的吸附较弱,产生的新吸附点位较少,主要通过竞争吸附作用抑制土壤对BTA的吸附.DOMbulk由78%的疏水组分构成,对土壤吸附BTA的影响与疏水组分相似.     

灭草松在土壤中吸附的支配因素

通过振荡平衡法测定了灭草松在6种土壤中的吸附等温线,计算了灭草松在吸附过程中平均偏摩尔自由能的变化值.结果表明灭草松在其中5种土壤上的吸附等温线为直线,分配常数Kd 0.14～0.31mL·g^-;土壤吸附灭草松的强弱次序为:德清水稻土＞安吉水稻土(pH4.79)＞余杭水稻土＞临安红壤＞安吉水稻土(pH7.36)＞德清黄壤.土壤性质与分配常数的相关分析,发现支配灭草松在土壤上吸附的主要因素是pH值和土壤有机质含量.灭草松在土壤上的吸附主要是中性灭草松及其阴离子在土壤有机质中的分配,与有机质性质关系不大.     

低分子量有机酸对几种可变电荷土壤吸附氟的影响

用一次平衡法研究了四种低分子量有机酸对几种可变电荷土壤吸附氟的影响，结果表明，低分子量有机酸可以通过竞争吸附作用抑制土壤对氟的吸附，化学结构相对简单的草酸和丙二酸对氟吸附的抑制作用大于柠檬酸和苹果酸。有机酸对氟吸附的抑制作用随土壤氧化铁含量的增加而增加，并随体系pH的增加而增强。在低pH和氟加入量较高的情况下，有机酸通过与氟竞争可溶性铝而增加土壤对氟的吸附量，这在对铝溶解度较高的酸性土壤中尤为明显。     

氯苯类化合物在沉积物上的非线性吸附行为

以5种自然沉积物为对象,采用批量平衡法,测定了氯苯、1,4-二氯苯、1,2,4-三氯苯和1,2,4,5-四氯苯在这5种沉积物样品上的吸附等温线,以研究沉积物自然有机质（NOM）的性质对氯苯类化合物（chlorobenzenes, CBs）吸附行为的影响.结果表明,1,2,4-三氯苯在虎门、黄沙、雅岗、三水、长洲5种沉积物中的等温吸附线性因子n都小于1,分别为0.956、 0.858、 0.872、 0.947和0.915,说明所有吸附等温线均为非线性;同时,非线性的程度n与极性指数（O+N）/C呈负相关关系,相关系数R²达0.994 7,表明NOM的聚合度（以极性指数为表征）直接影响着吸附非线性程度;5种沉积物对1,2,4-三氯苯的吸附亲和力（K_oc）随沉积物极性指数的增大而减弱,说明NOM聚合度较高的沉积物对1,2,4-三氯苯的吸附亲和力更强;氯苯、1,4-二氯苯、1,2,4-三氯苯、1,2,4,5-四氯苯在同一种沉积物（黄沙）上吸附等温线的线性因子n分别0.755、 0.788、 0.858、 0.949,非线性程度按溶质分子由小到大的顺序依次减弱,说明溶质分子本身的性质也影响着CBs在沉积物上的吸附性能.     

Biochar affects methylmercury production and bioaccumulation in paddy soils: Insights from soil-derived dissolved organic matter

Biochar has been used increasingly as a soil additive to control mercury (Hg) pollution in paddy rice fields. As the most active component of soil organic matter, soil dissolved organic matter (DOM) plays a vital role in the environmental fate of contaminants. However, there are very few studies to determine the impact of biochar on the Hg cycle in rice paddies using insights from DOM. This study used original and modified biochar to investigate their effect on DOM dynamics and their potential impact on methylmercury (MeHg) production and bioaccumulation in rice plants. Porewater DOM was collected to analyze the variations in soil-derived DOM in paddy soils. The results showed that the addition of biochar, whether in original or modified form, significantly reduced the bioaccumulation of MeHg in rice plants, especially in hulls and grains (p<0.05). However, MeHg production in soils was only inhibited by the modified biochar. Biochar addition induced a significant increase in DOM's aromaticity and molecular weight (p<0.05), which decreased Hg bioavailability. Furthermore, enhanced microbial activity was also observed in DOM (p<0.05), further increasing MeHg production in the soil. Thus, the effect of biochar on the fate of Hg cycle involves competition between the two different roles of DOM. This study identified a specific mechanism by which biochar affects Hg behavior in rice paddy soil and contributes to understanding the more general influence of biochar in agriculture and contaminant remediation.