菲、芘在单一和复合污染条件下不同老化阶段的提取率及其生物有效性

研究了土壤中多环芳烃菲、芘在单一和复合污染条件下的老化过程,150天内观察到菲、芘的提取率随时间延长而逐渐减少,下降速率呈现初始较快、而后减慢的趋势;菲、芘的环糊精提取法的提取率随老化时间延长而下降的趋势要比索氏提取法明显。老化过程中复合污染土壤中芘的索氏法提取率略低于单一污染土壤中芘的提取率。在老化的后期,复合污染土壤中菲的环糊精法提取率略高于单一污染土壤中菲的提取率。利用蚯蚓作为测试生物,研究两种污染物的老化过程对其生物有效性的影响,发现表征其生物有效性的蚯蚓吸收率、生物富集系数(BCF)均随老化时间的延长而下降,此外,老化过程中复合污染条件下菲的生物有效性总是大于菲作为单一污染源时的生物有效性。对污染物的环糊精法提取率和蚯蚓吸收率作相关分析发现,单一污染土壤中菲和芘的环糊精提取法的提取率与蚯蚓吸收率均呈显著正相关。     

残留农药的生物有效性研究进展

生物有效性,即为衡量生物摄取摄取土壤中污染物的可能性的标准,同时,是影响污染物在环境中降解或转化等环境行为及其对非靶标生物危害性的重要参数总和。20世纪以来,污染物的生物有效性问题已成为农业科学与环境科学和生态学的热点研究问题。由此,拟对这一课题进行初步探索。     

土壤中多氯联苯的生物有效性及其影响机制研究

多氯联苯(PCBs)属于环境中广泛存在的持久性有机污染物(POPs),威胁生态系统安全与人体健康。为评价典型土壤中PCBs的生态风险,揭示其生物有效性以及影响生物有效性的分子机制将具有重要科学意义。本文以赤子爱胜蚓(Eisenia fetida)为土壤模式生物,模拟土壤中6种典型PCBs化合物(PCB-18、PCB-20、PCB-28、PCB-101、PCB-105、PCB-114)的富集动力学过程,并分析了蚯蚓吸收累积对土壤中PCBs总量的影响。结果表明,对于PCB-18、PCB-20和PCB-28,蚯蚓富集15天能够达到动力学过程的近平衡状态,而PCB-101、PCB-105和PCB-114则在30天达到近平衡状态,这可能是由于分子体积增大致使PCBs自由穿越生物膜并为生物体有机脂相富集的过程受到一定程度的限制,吸收速率变慢。PCBs生物有效性与典型分子性质(α、Kow)之间高度线性相关,从微观层面上揭示了影响生物有效性的分子机制,进一步表明PCBs分子体积、分子极化率及其疏水作用是影响生物有效性的主要因子,为典型土壤中PCBs污染物的生态风险预测与评价提供科学依据。     

六氯苯在土壤中的主要迁移转化过程

六氯苯(HCB)是环境中典型的持久性有机污染物(POPs)。土壤是HCB的主要贮存场所,研究土壤中HCB的迁移转化规律对揭示其环境效应有重要意义。本文从以下几方面综述了土壤中HCB的主要迁移转化过程:土壤中累积的HCB不断向大气挥发而造成空气污染;土壤对HCB的吸附影响其在环境中的迁移转化速率;HCB通过多种化学键与土壤形成结合残留,暂时降低其生物有效性;厌氧条件下,HCB可发生还原脱氯降解,使其毒性和持久性大大降低。本文最后展望了关于土壤中HCB迁移转化的下一步研究方向。     

外源铜在土壤中的老化研究进展

水溶性Cu添加到土壤后,其可浸提性、生物有效性或毒害随时间逐渐降低,这个过程称为老化过程.田间污染土壤中的Cu与人工新添加的Cu在生物有效性上存在着明显的差异,因此,在生态风险评价和环境质量标准制定中,考虑Cu的老化过程显得十分必要.而且,它对污染土壤的管理和修复也有重要的指导意义.本文详细综述了外源Cu在土壤中的老化机理及影响因素,指出老化过程主要受扩散作用、聚合/沉淀作用和包裹作用共同控制,而且在长期老化阶段,微孔扩散成主导作用机理;pH、温度、有机质和土壤类型是老化的主要影响因子,其中pH影响聚合/沉淀作用和扩散作用,温度主要影响扩散作用,而有机质对上述各个机理都有影响.     

表面活性剂对老化土壤中PAHs的生物有效性的影响

采用聚2,6-二苯基对苯醚(poly(2,6-diphenyl-p-phenylene oxide),Tenax-TA)提取和蚯蚓(Eisenia Fetida)富集实验研究曲拉通-100(聚乙二醇辛基苯基醚,Triton X-100)、吐温-80(聚氧乙烯脱水山梨醇油酸酯,Tween-80)和羟丙基-β环糊精(HPCD)表面活性剂对老化农田土壤中多环芳烃(PAHs)可提取组分以及生物有效性的影响。结果显示,表面活性剂可以显著增加PAHs的可提取性和在蚯蚓体内的蓄积浓度;和对照相比,增加可提取性42.3%~269%,蚯蚓体内的蓄积量增加10%~340%。研究表明在使用表面活性剂进行土壤修复时老化PAHs类污染物可能重新释放到环境中并带来环境风险。     

农田土壤中生物质炭的老化及其对有机污染物吸附-解吸影响的研究进展

生物质炭独特的表面性质、形貌结构及丰富而离散的孔隙系统使其对有机污染物具有良好的持留与吸附作用,可望用于土壤污染控制与修复。在田间条件下,进入土壤的生物质炭自身不稳定组分会发生转化、淋溶,并与土壤发生相互作用出现老化现象,导致生物质炭的化学与物理性质发生显著变化。生物质炭在土壤中的老化过程具有复杂性和多样性,主要包括:生物质炭化学性质的变化,如无机元素的流失、表面官能团组成的变化以及部分矿化反应;生物质炭物理性质的改变,主要是土壤有机质和矿物质对生物质炭的包覆作用造成生物质炭的孔隙特征发生改变。生物质炭在土壤中的老化可能会导致有机污染物的吸附-解吸行为发生改变,且受土壤、生物质炭以及污染物性质的影响较大。本文综述了生物质炭在农田土壤中的老化机理及主要影响因素研究方面的进展,总结了生物质炭在土壤中的老化对有机污染物吸附-解吸行为的影响,提出了尚待解决的相关前沿科学问题。     

农田土壤-植物系统持久性有机污染物的界面过程与自修复——以多氯联苯为例

土壤-植物系统是地球陆地表层生态系统中非常重要的亚系统,对保障粮食安全与人体健康发挥着关键作用。持久性有机污染物是土壤环境中难降解、长残留的毒害污染物。这类有机污染物在土壤组分、土壤微生物和植物的共同作用下,发生着一系列的物理化学与生物学的界面过程,导致其或者生物有效性的降低和毒性的下降,或者快速降解,进而减少在食物链中传递的风险,达到自然条件下土壤污染净化,实现自修复。以多氯联苯为例,综述了农田土壤-植物系统中持久性有机污染物的土壤组分界面过程、根际界面过程和植物体微界面过程研究进展,提出了发挥土壤-植物系统降解净化作用,实现持久性有机污染物自修复的新思路。参30。     

根-土界面的微生态过程与有机污染物的环境行为研究

土壤-植物系统是地球生态系统中与人类生存与健康关系最为密切的亚系统。该系统中有机污染物的运移必须历经根-土界面多层次的微生态过程的控制。这些微生态过程涉及到系统中许多生物、生物化学和物理化学反应机理,与土壤中污染物迁移转化及其归宿等环境行为具有密切的关系。理解这些微生态过程及其对有机污染物环境行为的影响,对提高作物生长、改善土壤环境质量和提高农产品品质安全具有直接的理论和实践指导意义。     

阳离子表面活性剂增强固定土壤中的苯酚和对硝基苯酚

当前,对有机物污染土壤进行修复成为环境科学研究热点之一[1],常用的修复方法有化学修复、生物修复、化学与生物相结合的修复;但迄今仍没有经济有效的有机污染土壤修复的实用技术.因此,利用在土壤中注入阳离子表面活性剂形成吸附区,截留有机污染物,阻止有机物迁移,并对固定污染物进行修复,无论对土壤及地下水有机物污染防治,还是生产优质农产品都具有现实意义.近年来,相关研究主要集中在截留非极性有机污染物[2～7],而对溶解度较大且易于迁移的极性有机物截留研究较少;并且认为表面活性剂增强土壤截留有机物的机理由土壤表观有机碳含量增大所致.对硝基苯酚、苯酚是环境中优先控制有机物,它们是重要化工原料,也是农药的降解产物.本文以极性化合物对硝基苯酚、苯酚为目标污染物,探讨阳离子表面活性剂增强固定作用及机理,为有效防治土壤有机污染提供理论依据.     

Availability of Pyrene in Unaged and Aged Soils to Earthworm Uptake, Butanol Extraction and SFE

Eco-risk of an organic pollutant in soil is quite influenced by the property of the soil and contamination history. To evaluate the influence of these factors on the availability of organic pollutants, earthworm accumulation of pyrene in six different soils were studied in this paper used unaged and aged samples. Moreover, butanol extraction and supercritical fluid extraction (SFE) of pyrene in these samples were determined simultaneously, and the relationship between bioaccumulation and extraction by butanol and SFE before and after aging were investigated in order to find a rapid method to predict the bioavailability. The results showed that, for unaged samples, percentages of pyrene accumulated by the earthworms (Eisenia foetida), extracted by butanol and mild supercritical fluid were 1.9–18.5%, 41.8–50.8% and around 50%, respectively. Generally, the percentages of the earthworm accumulation decreased significantly and butanol extraction decreased slightly with the content of soil organic matter (SOM) in soils. Clay content might also influence pyrene availability when SOM content is smaller than 1%. However, mild SFE could not differentiate the availability of the pyrene in unaged soils. Both the bioavailability and the chemical availability of pyrene decreased significantly after aged in soils for 120 days, and the percentages of availability by the three test methods were 0.87–3.65%, 18.7–27.6% and 12.9–28.2%, respectively. A correlation relationship study of pyrene extractability by butanol and mild SFE with bioavailability to earthworm uptake for aged soils suggested that mild SFE was a better approach to predict the bioavailability of organic chemicals in field soils compared to butanol extraction.     

水分非饱和条件下土壤矿物界面有毒有机物转化机制研究进展

土壤矿物作为土壤重要活性组分，可驱动土壤有毒有机物化学转化，降低污染风险。以往土壤矿物与有毒有机物界面行为研究主要集中于水环境或矿物悬浊液体系，然而实际环境中土壤及其矿物常处于干燥、湿润等水分非饱和状态。近年来，水分非饱和条件下土壤矿物界面有毒有机物转化及机制已成为研究热点，相关研究获得一系列新发现。低含水量铁锰矿物、黏土矿物和金属离子饱和黏土矿物能驱动多环芳烃、抗生素等疏水性有毒有机物化学转化。水分非饱和环境会减弱矿物界面水分子与有毒有机物竞争活性位点，并使矿物发生脱水、向高活性结构转变。此外，土壤矿物水分状态也会影响有毒有机物转化产物，水分非饱和环境更有利于持久性自由基和卤代二噁英等中间产物的形成和稳定。以往研究认为，电子转移反应是土壤矿物界面有毒有机物转化机制，随着检测技术与理论计算的发展，自由基催化和水解作用机制逐渐被发现，相关机制研究精准至矿物晶型和晶面层面。虽然水分非饱和条件下土壤矿物界面有毒有机物转化及机制已逐渐清晰，但其研究广度和深度有待进一步拓宽和加深。建议未来在实际水分非饱和土壤和矿物中开展有毒有机物转化研究，深入探究还原转化过程，研发原位反应装置及检测方法，尝试从微纳米尺度和分子水平解析有毒有机物在矿物界面转化机制。     

Earthworms (Eisenia foetida, Savigny) mucus as complexing ligand for imidacloprid

Earthworms can excrete copious amounts of mucus that may affect the fraction, transport fate, and bioavailability of contaminants in soil. However, interaction of mucus with organic contaminants is still not well-known. In the present study, complexation properties of surface mucus (from the earthworm species Eisenia foetida, Savigny) with imidacloprid were investigated using fluorescence excitation emission matrix (EEM) spectroscopy. It was found that carbohydrates and proteins are major components in mucus of this species. Two fluorescent peaks belonging to protein-like substances were identified in the EEM spectrum of mucus. The protein-like fluorescence was clearly quenched by imidacloprid, indicating that the protein-like substances reacted strongly with imidacloprid. The fluorescence quenching processes was governed by a static process. The values of effective quenching constant (logK _a) for these two peaks were 11.46 and 7.96, respectively, indicating that there is a strong interaction between mucus and imidacloprid and mucus–imidacloprid complexes are formed. Higher binding constants (logK _b?=?25.6 and 14.0) than those for heavy metals binding to dissolved organic matter or organic pollutants binding to proteins confirm the strong complexation between mucus and imidacloprid. Our study implies that earthworm surface mucus may significantly affect the fraction, toxicity, and bioavailability of organic contaminants in the soil due to its high affinity for organic contaminants.     

Enhanced Biodegradation of Naphthalene and Anthracene by Modified Vermiculite Mixed with Soil

Hydrophobic modified vermiculite mixed with soil was investigated in biodegradation experiments of naphthalene and anthracene. The experiments had been carried out on mixtures of soil and vermiculite at a proportion of 2%, 10%, and 15% and also in the absence of clay used for control. Biodegradation of the pollutants was followed by the decline of naphthalene and anthracene concentration, measured by CG. Compound mineralization was also proved by the evolution of CO₂. The results showed that in the mixture with a higher proportion of vermiculite biodegradation is enhanced compared to that performed in the absence of vermiculite. In general, when vermiculite proportions are increased, the rate of degradation increases, which may account for the bioavailability of compounds. Bioavailability is an important factor for the degradation of compounds with low solubility. Comparison of biodegradation rates shows that naphthalene is degraded faster than anthracene. The chemical structure could be responsible for this observation. However, although we did not identify the microorganism that was in the soil, we can conclude that vermiculite could be an alternative for the bioavailability of such compounds. Vermiculite in the modified form could also be very useful as a barrier to retain organic pollutants in accidental spills.     

天然有机添加物提高植物修复污染土壤效率：研究进展综述.

Environmental pollution caused by metals, radionuclides and organic pollutants affects quality of the biosphere: soil, water and air.Currently, great efforts have been made to reduce, remove or stabilize contaminants in polluted sites. There has been increasing interest in phytoremediation—the use of plants to reduce concentration of pollutants or to render them harmless. This paper provides a brief review of recent progress in the research and practical application of phytoremediation techniques. Improvements in phytoremediation due to utilization of organic amendments, namely, agro- and industrial wastes(such as sugar beet residue, composted sewage sludge or molasses), biochar, humic substances, plant extracts and exudates are discussed, as well as their influences on soil structure and characteristics, plants growth and bioavailability of pollutants. Both plant-assisted phytoremediation and the use of natural materials in the absence of remediating plant are believed to be cost-effective and environmentally friendly approaches for soil cleanup. However,the characterization and quantification of a range of natural materials used in phytoremediation are essential in order to implement these approaches to practice.     

持久性有机污染物的根际修复及其研究方法

根际是具有特殊性质的土壤微生态环境,对土壤中持久性有机污染物的行为及生物修复具有重要作用。本文从微生物降解、植物过程、非生物降解、土壤吸附、挥发、淋溶等方面归纳了有机污染物根际修复的研究进展,并从细胞培养、添加根系分泌物或根系残留物、挥发污染物收集和残留态污染物测定等方面综述了有机污染物根际行为的研究方法及其优缺点。     

土壤有机污染物电化学修复技术研究进展

综述了有机污染土壤的电动力修复和微生物电化学修复的最新研究进展。分析了电动力修复中电极材料、运行条件等因素对污染物去除效果的影响,总结了添加表面活性剂、引入具有降解能力的基质、与化学或生物联合等方式对土壤修复效果的强化作用,阐述了微生物电化学修复的效果、影响因素和微生物群落演变的规律。电化学技术能够有效去除土壤中的有机污染物,且电动力较微生物电化学具有更好的去除效果。为了实现电化学技术在污染土壤修复中的应用,未来需要从土壤导电性、电极材料以及反应器构型等方面优化以提高修复效果;此外,电化学修复技术的机理、功能微生物的群落特征研究等也是下一步研究的重点。     

施用猪粪对不同类型土壤中铜的赋存形态及小白菜吸收铜的影响

  目的  探讨猪粪中铜（Cu）的输入对土壤中Cu的赋存和生物有效性的影响。  方法  将1%和3%的腐熟猪粪（干猪粪∶秸秆 = 10∶1）添加到黄褐土、红壤、黑土、褐土中,分别老化0、1、2、3、5个月后,进行小白菜盆栽实验。  结果  与对照相比,施用猪粪使黄褐土、红壤、黑土和褐土土壤铜（Cu）全量分别显著增加了20.23% ~ 50.43%、79.87% ~ 142.6%、52.41% ~ 76.43%和41.14% ~ 92.24%。四种土壤中水溶态（F1）、碳酸盐结合态（F3）Cu占比均增加,施用3%猪粪的红壤未老化处理中F1-Cu和黄褐土未老化处理中F3-Cu增幅最大,分别达4.55%和16.47%。土壤铁锰氧化态（F5）、有机结合态（F6）Cu占比增加,残渣态（F7）占比降低。土壤有效态Cu的占比与猪粪老化时间呈显著负相关,3%猪粪老化5个月处理的黄褐土、黑土和褐土土壤有效态Cu占比分别降低12.85%、4.11%和3.68%,而红壤有效态Cu占比随老化时间变化不显著。在黄褐土中,腐殖酸结合态（F4）Cu的占比随猪粪老化时间的延长逐渐增加。施用猪粪显著增加小白菜对Cu的吸收,其中红壤的增幅最大,根系与地上部Cu含量分别显著提高244.5%和381.7%,地上部Cu含量为国家食品中污染物限量标准的1.44 ~ 2.56倍。逐步回归分析方程表明小白菜根系Cu的含量与土壤pH、粘粒及腐殖酸结合态（F4）含量呈显著负相关,与猪粪Cu输入量、土壤可溶性有机质含量呈显著正相关。  结论  猪粪的Cu输入显著提高土壤和小白菜的Cu 含量。土壤Cu的生物有效性不仅受土壤性质的影响,猪粪本身及在土壤中分解产生的腐殖酸和水溶性有机质对Cu的有效性也有较大的影响。通过比较不同的土壤类型,施用含Cu猪粪在红壤－作物系统中存在相对较高的重金属污染风险。     

生物质炭修复重金属及有机物污染土壤的研究进展

生物质炭是生物质原料在完全或部分缺氧条件下高温热解后的固体产物,它具有丰富的孔隙结构和较高的碳含量。该物质具有巨大的表面积和较强的阳离子交换能力等特殊性质,对受污染土壤中的重金属和有机物都具有很强的吸附能力,有效地降低这些污染物的生物有效性和在环境中的迁移,对改善土壤环境具有重大意义。近年来我国土壤污染严重,利用生物质炭修复受污染土壤的技术得到了广泛的关注。本文简述了生物质炭修复土壤污染的基本原理,探讨了与其他修复方法相比存在的优势,阐述了国内外近年来利用生物质炭修复污染土壤的研究进展,最后展望了今后需要进一步研究的领域。     

The Influence of pH and Organic Matter from Sugarcane By-products on Soil Cadmium Fractionation

ABSTRACT

Crop wastes or by-products can have the potential to be used as effective amendments to improve agricultural soil quality and/or crop yields subject to appropriate screening and testing. Sugarcane (Saccharum officinarum L.) waste by-products from an ethanol production plant, including boiler ash, filter cake, and vinasse, were applied as soil amendments at 5%, 10%, 20%, and 40% (w/w) to study the relationship between pH and organic matter (OM) on cadmium (Cd) bioavailability and adsorption via organic matter using the Cd sequential extraction procedure. Soil pH was significantly affected by aging of the treatment with boiler ash, filter cake, and vinasse. At the end of the experiment, the Cd concentrations with all treatments were mainly released in the first two extraction steps of the sequential procedure, i.e., most mobile and easily mobilized fractions. Pearson correlation analyses revealed a negative relationship between pH and bioavailable Cd and between OM and oxidizable Cd. The pH reduction induced by the amendments was a major factor affecting soil Cd bioavailability. The effect of OM on Cd fractionation could not be clearly observed and interpreted in this study.