有机质官能团及微孔特性对疏水性有机污染物吸附的影响机制

作为重要的地质吸附剂,土壤/沉积物中的有机质是环境中疏水性有机污染物主要的汇.由于有机质的结构异质性,疏水性有机污染物一旦进入其中,会被吸附在不同的位点上,反应活性和生态风险进而会发生变化.对疏水性有机污染物在有机质上的吸附进行研究有助于了解其在环境中的分布,传输及生物有效性.本文就疏水性有机污染物在土壤/沉积物中的有机质上吸附的国内外研究进展进行了综述,讨论了重要有机质组分(腐殖质和碳黑)的结构和吸附作用差异性,重点分析了有机质的微孔特性和官能团对吸附的影响机制.     

通讯

邻苯二甲酸酯在不同来源黑碳上的吸附特征研究黑碳是生物体或化石燃料不完全燃烧而产生的一种含碳的混合物,其结构致密,具有高度芳香化结构,在沉积物和土壤中广泛存在,并且作为一种吸附能力很强的有机碳组分受到人们的高度关注,成为当前研究的热点.但目前研究主要集中于黑碳对多环芳烃,多氯联苯等平面结构有机物的吸附,而有关非平面疏水性有机物在黑碳上吸附特性和吸附机理的     

土壤和沉积物中疏水性有机污染物的锁定及其环境效应

大量研究表明,吸附到土壤和沉积物中的疏水性有机物只有部分能够较容易地解吸出来,而残留的部分很难解吸.这种现象常被称为"解吸滞后","不可逆吸附",或者"锁定".锁定会导致受污染土壤和沉积物修复效率的降低;但与此同时,锁定也会降低受污染土壤和沉积物的环境风险.本文综述了土壤和沉积物中疏水性有机污染物锁定的典型热力学和动力...     

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。     

典型环境内分泌干扰物的来源、环境分布和主要环境过程

内分泌干扰物(EDCs)作为一种新兴污染物,具有憎水性、低剂量效应和半衰期长等特征,在全球的土壤/沉积物中已被广泛检测到,并发现已给环境带来了严重的威胁。本文重点综合评述了近10年来土壤/沉积物中EDCs的来源、浓度水平、空间分布及吸附特性的研究。结果发现,EDCs来源涉及农业、工业和生活等多个方面;空间分布上,一般呈近海地区沉积物中EDCs浓度水平较河流底泥及土壤低,而高度工业化、城市化地区土壤/沉积物中EDCs浓度亦较高;EDCs的吸附受土壤/沉积物理化性质、EDCs自身性质和环境条件的共同影响,一般土壤有机质的含量和成熟度、土壤颗粒的比表面积与其吸附能力呈正相关,黏土矿物类型对EDCs的吸附也有重要的影响;EDCs的吸附能力与其自身的疏水性和结构特征有关;温度升高和溶液p H值增加都不利于EDCs的吸附,而溶液离子强度的增加对其吸附起着促进作用。土壤/沉积物对EDCs的吸附是一个复杂的过程,因此对其吸附特性需要进一步的探讨。     

中国土壤与沉积物中邻苯二甲酸酯污染水平及其吸附研究进展

邻苯二甲酸酯（PAEs）是一类重要的环境激素化合物,具有致畸性、致癌性、致突变性及生殖毒性的特点。在环境中普遍存在,对人体及生态环境的威胁极大,已经引起了人们广泛的关注。吸附作用是影响污染物在土壤及沉积物环境中迁移转化的关键因素之一。分析了近年来我国土壤及沉积物中PAEs的污染现状,归纳了影响PAEs吸附过程的主要因素。我国与世界其他各国的土壤及沉积物的PAEs主要污染组分较为一致,但PAEs污染相对严重。土壤有机质及粘土矿物对PAEs的吸附影响成为了学术界的研究热点。有机质中的腐殖质对PAEs的吸附起着决定作用;腐殖质由胡敏酸、富里酸及胡敏素,部分含有碳黑组成,各组成对PAEs的吸附影响大小不一,相应的吸附机理还有待于深入的研究,而且土壤与沉积物中的溶解性有机物（DOM）对PAEs的吸附双重影响认识还不够。在有机质含量低的土壤中,粘土矿物对PAEs的吸附起着主要作用,然而PAEs的吸附与粘土矿物类型及其表面电场的关系、是否能与水分子竞争表面电场等问题还不甚清楚,需要进一步探索。今后将引入并开发先进的分析测试技术,从土壤及沉积物的有机质组成及微观结构研究其对PAEs的吸附机理。     

土壤和沉积物的有机质组分对水中非离子有机物吸着的影响

在２５℃下，分别测定来自水各地的四种土壤和八种沉积物吸着水溶液中的１，２－二氯苯和四氯化碳的吸附等温线，所有的等温线呈线性，表明土壤和沉积物吸着水溶液中的非离子有机物的过程是分配机理，土壤或沉物的本身用有机碳标化的吸附系数（Ｋｏｃ）之间差异不大，而土壤的和沉积物之间的Ｋｏｃ则存在显著性差异，这是由于沉积物有机质成分的极性小于土壤有机质成分的极性造成的，沉积物质吸着上述两种有机物的Ｋｏｃ约是土壤的Ｋ     

黑碳对土壤和沉积物中菲的吸附解吸行为及生物可利用性的影响

利用淡水单孔蚓Monopylephorus limosus的生物富集实验,研究了黑碳对土壤和沉积物中多环芳烃类有机化合物菲生物可利用性的影响,同时研究了黑碳对菲吸附和解吸行为的影响,并用"双元平衡解吸(DED)模型"对解吸行为进行了预测.结果表明,土壤和沉积物中黑碳的存在直接导致了菲在颤蚓体内的生物累积因子(BSAF)的降低,其原因在于菲在黑碳沉积物样品中的不可逆吸附程度的显著增强.研究发现,土壤和沉积物中菲的生物可利用性与土壤和沉积物中菲的吸附相浓度无关而与孔隙水浓度密切相关.     

模拟酸雨对工业污染场地表层土壤中多环芳烃释放的影响

通过工业污染场地表层土壤的模拟酸雨浸泡试验,分析了不同酸度的模拟酸雨浸泡前后土壤中有机质、EPA优先控制的16种多环芳烃含量和矿物质组成的变化.研究结果表明,酸雨浸泡前后土壤矿物相组成相似,主要以石英为主,只是在矿物组成的量上存在差别,浸泡后土壤中赤铁矿和粘土矿物的含量较浸泡前有所减少.模拟酸雨浸泡后土壤中有机质和多环芳烃均有不同程度的释放,酸雨pH值越小,释放量越大,且多环芳烃可能是随着有机质一起释放的;酸雨对土壤中不同性质多环芳烃释放的影响不同,对低环多环芳烃（环数≤3）释放的影响较大,对高环多环芳烃（环数≥4）影响较小.研究结果为理解在酸雨作用下工业污染场地土壤中多环芳烃的释放规律及土壤中多环芳烃稳定性研究提供一些科学依据.     

疏水性有机污染物在土壤/沉积物中的赋存状态研究

土壤/沉积物是环境中有机污染物主要的汇,由于土壤-沉积物结构和性质的复杂性,有机污染物进入其中,会结合在不同的位点上,赋存状态发生分化,具有不同的物理流动性、生态风险和化学反应活性.对于土壤-沉积物中有机污染物吸附/解吸的研究是认识其赋存状态并预测其生态风险的重要手段.本文对于疏水性污染物吸附/解吸及赋存状态的国内外研...     

Controlling microbiological interfacial behaviors of hydrophobic organic compounds by surfactants in biodegradation process

Bioremediation of hydrophobic organic compounds （HOCs） contanlinated soils involves several physicochemical and microbiological interracial processes among the soil-water-microorganism interfaces. The participation of surfactants facilitates the mass transport of HOCs in both the physicochemical and microbiological interfaces by reducing the interfacial tension. The effects and underlying mechanisms of surfactants on the physi-cochemical desorption of soil-sorbed HOCs have been widely studied. This paper reviewed the progress made in understanding the effects of surfactant on microbiological interlhcial transport of HOCs and the underlying mechanisms, which is vital for a better understanding and control of the mass transfer of HOCs in the biodegradation process. In summary, surfactants affect the microbiological interfacial behaviors of HOCs during three consecutive processes： the soil solution-microorganism sorption, the transmembrane process, and the intracellular metabolism. Surfactant could promote cell sorption of HOCs depending on the compatibility of surfactant hydrophile hydrophilic balance （HLB） with cell surface properties; while the dose ratio between surfactant and biologic mass （membrane lipids） determined the transmembrane processes. Although surfactants cannot easily directly affect the intracellular enzymatic metabolism of HOCs due to the steric hindrace, the presence of surfactants can indirectly enhanced the metabolism by increasing the substrate concentrations.     

Assessment of persistent organic pollutants in soil and sediments from an urbanized flood plain area

Polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and phenolic compounds (PCs) are persistent organic compounds. Contamination of these potentially toxic organic pollutants in soils and sediments is most studied environmental compartments. In recent past, studies were carried out on PAHs, OCPs and PCs in various soils and sediments in India. But, this is the first study on these pollutants in soils and sediments from an urbanized river flood plain area in Delhi, India. During 2018, a total of fifty-four samples including twenty-seven each of soil and sediment were collected and analyzed for thirteen priority PAHs, four OCPs and six PCs. The detected concentration of ∑PAHs, ∑OCPs and ∑PCs in soils ranged between 473 and 1132, 13 and 41, and 639 and 2112 µg/kg, respectively, while their concentrations in sediments ranged between 1685 and 4010, 4.2 and 47, and 553 and 20,983 µg/kg, respectively. PAHs with 4-aromatic rings were the dominant compounds, accounting for 51 and 76% of total PAHs in soils and sediments, respectively. The contribution of seven carcinogen PAHs (7CPAHs) in soils and sediments accounted for 43% and 61%, respectively, to ∑PAHs. Among OCPs, p, p’-DDT was the dominant compound in soils, while α-HCH was found to be dominated in sediments. The concentrations of ∑CPs (chlorophenols) were dominated over ∑NPs (nitrophenols) in both the matrices. Various diagnostic tools were applied for the identification of their possible sources in soil and sediments. The observed concentrations of PAHs, OCPs and PCs were more or less comparable with the recently reports from various locations around the world including India. Soil quality guidelines and consensus-based sediment quality guidelines were applied for the assessment of ecotoxicological health effect.

     

基于Tenax脱附技术评价沉积物中不同碳质对菊酯类农药生物有效性的影响研究

本文选取泥炭、生物质炭、木炭和活性炭4种含碳材料,结合以经济底栖生物菲律宾蛤仔(Venerupis philippinarum)为受试生物的生物累积实验和Tenax连续萃取法,阐述不同碳质对沉积物中4种菊酯类农药生物有效性的影响,并将Tenax萃取结果与底栖生物的累积结果进行了相关分析。结果表明,碳质的添加导致沉积物中菊酯类农药的快速脱附组分(Frap)降低,极慢速脱附组分(Fv s)增大,生物有效性降低,且4种碳质对Frap的影响有所不同,然而因为菊酯类农药的理化性质,Frap的差异并不显著。Tenax 6 h和24 h的单点萃取组分与快速脱附组分相关性显著(P0.0001),基本可以代替完整的脱附动力学评价生物有效性,但是对于组成复杂,有机碳(OC)和黑炭(BC)含量高的沉积物进行研究评价时仍应注意由此产生的偏离。Tenax快速脱附组分与2种底栖生物累积结果之间具有显著的相关性(R2=0.38,P0.0001),表明在OC和BC含量不同的沉积物中,Tenax萃取技术也可以预测菊酯类农药在经济底栖生物菲律宾蛤仔体内的累积量,进而为沉积物中HOCs的环境质量和相关水产品的质量评估提供更为快捷、有效的参考依据。     

土壤和沉积物中非水解有机碳对菲的吸附

采用改进的酸水解方法对土壤和沉积物中的有机质组分进行了分离和提取,用固体13C核磁共振（13CNMR）表征了非水解有机碳（NHC）,同时研究了不同有机质组分对菲的吸附行为,结果表明,菲的吸附等温线都呈现出明显的非线性,能很好地拟合Freundlich方程;而且NHC和碳黑（BC）比其原始和去矿样品的吸附容量都有明显提高.这些结果揭示了NHC和BC主要控制着菲在土壤和沉积物中的吸附行为.沉积物及其NHC对菲的吸附容量要高于土壤及其NHC,这与土壤和沉积物中有机质的不同来源有关.     

土壤和沉积物中的聚合有机质对多环芳烃分布和提取的影响

为了研究土壤和沉积物中凝聚型有机碳(碳黑、干酪根)的含量及其对多环芳烃(PAHs)分布和提取的影响,分别用三氟醋酸(TFA)和在375℃下通氧燃烧的方法从珠江三角洲2个污染土壤和5个河口沉积物样品中提取酸非水解有机碳(NHC)和碳黑(BC);用索氏抽提法和不同溶剂的加速溶剂萃取法(包括连续加速萃取法ASESum和标准溶剂萃取法ASESTD)抽提土壤和沉积物中的多环芳烃,并在不同温度梯度(25℃到150℃)下用水为溶剂加速溶剂萃取其水溶态.结果表明,1)NHC是珠江三角洲土壤和沉积物中总有机碳的重要组成部分,NHC碳明显高于BC碳,NHC和BC分别占土壤和沉积物中有机碳的25.6%￣73.8%和4.64%￣17.3%.2)3种有机溶剂(丙酮、甲苯1、甲苯2)连续抽提的PAHs含量是索氏抽提的2.11倍;5种ASE方法(丙酮、甲苯1、甲苯2、ASESum、ASESTD)提取的PAHs含量与NHC含量存在明显的相关性,而且比PAHs含量与BC或无定型有机碳(AOC)含量的相关性更明显.3)在不同温度梯度下水溶态PAHs浓度符合Van’tHoff方程.研究说明除了BC外,非水解有机碳对土壤和沉积物中PAHs的分布和提取具有重要影响.     

Pyrene partition behavior to the NOM: Effect of NOM characteristics and its modification by ozone preoxidation

Hydrophobic organic contaminants (HOCs)—pyrene, and natural organic matters (NOM) from different sources were taken as the test compounds to investigate the impact of physicochemical characteristics of NOM on HOCs’ partition to the NOM in this study. The effects of solution property, NOM characteristics, and modification by ozone preoxidation on pyrene partition to NOM were systematically evaluated. According to the fluorescence quenching method, the partition coefficient K _oc of pyrene to NOM was calculated, which was found to have a great relationship with the aromatic structures and hydrophobic functional groups of the NOM. The NOM characteristic modification corresponding to solution property could influence the interactions between the NOM and pyrene. Preozonation could destroy the aromatic or hydrophobic structures of the NOM and decrease K _oc of pyrene.     

多环芳烃生物修复中的表面活性剂

由于其致癌、致突变和致畸性，多环芳烃(PAHs)成为环境中一类重要的有机污染物。生物修复是一种经济和有效的修复污染土壤的方法。由于PAHs低的水溶性、强的吸附性，使其生物可利用性降低，不利于生物修复。添加表面活性剂是一种常见的加强PAHs生物利用性的方法。文章概述了近年来在多环芳烃生物修复中关于表面活性剂的研究进展。     

Sorption of DDTs on biofilms, suspended particles and river sediments: effects of heavy metals

The sorption by solid materials is one of the most important processes that affect the fate of hydrophobic organic pollutants in aquatic systems. Current studies focus on the sorption of hydrophobic pollutants by single natural solid material, whereas few studies compared the sorption behaviors of different solids. Furthermore, natural aquatic environment is a complex system where hydrophobic pollutants coexist with many other pollutants, but only limited studies reported the effects of coexisting components on the sorption. Here we studied the sorption of dichlorodiphenyltrichloroethanes (DDTs) by three common solids in natural water, i.e., biofilms, suspended particles and sediments. The effects of typical coexisting heavy metals on the sorption were also examined. The results show that the sorption is described by a dual-mode sorption model. Compared with sediments, more DDTs were sorbed by biofilms and suspended particles. Coexisting Pb, Cd and Cu increased the sorption of DDTs on sediments while decreasing the sorption on biofilms slightly, with little effect on the sorption on suspended particles. The different sorption behaviors of the solids were mainly determined by the composition of the solids: more organics were observed in biofilms and suspended particles.     

Evidence for a mutual effect of biofilms, suspended particles and sediments on DDT sorption

This report shows that biofilms and suspended particles double DDT sorption capacity on surface sediments. Sorption of pollutants by solid materials, such as biofilms, suspended particles and sediments, is a major process controlling the fate of hydrophobic pollutants in natural waters. Most previous studies focused on the sorption of hydrophobic pollutants by single-solid material, whereas few studies considered the mutual effect of different solids on the sorption. Various solid materials often interact with each other when they coexist in the same system. Therefore, pollutants sorption could be different from that in the single-solid sorption system. Here we studied the mutual effect of biofilms, suspended particles and surface sediments on the sorption of dichlorodiphenyltrichloroethane (DDT). Results showed that biofilms and suspended particles double DDT sorption capacity on surface sediments. The different effects were mainly determined by distinct components and structures of the three solid materials, particularly by organic components. Here we show the mutual effect of biofilms, suspended particles and sediments on DDT sorption.     

Sorption of tetracycline to sediments and soils: assessing the roles of pH,the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL^- and L^2-). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.