河流湿地土壤芘的降解和生物有效性模型与酶活性动态变化(Model of Pyrene Degradation and Bioavailability and Dynamic Changes of Enzymatic Activities in the Riverine Wetland Soil)

在淹水和非淹水条件下,在河流湿地土壤中加入高浓度(10mg·kg-1)和极高浓度(200mg·kg-1)芘,研究了芘降解过程、芘生物有效性和土壤酶活性的长期动态变化.结果表明,培养91d后,高浓度芘处理的土壤中芘的残留率在淹水和非淹水条件下分别为79.0%和51.4%,而极高浓度处理的芘残留率在淹水和非淹水条件下分别为61.1%和33.9%.利用Tenax-ta树脂提取快速解吸态生物有效芘,结果发现,有效芘浓度在高浓度芘处理的两种土壤中的值比较接近,分别为1.01mg·kg-1和1.23mg·kg-1;而有效芘浓度在极高浓度处理的两种土壤的相应值差别较大,分别为20.31mg·kg-1和9.44mg·kg-1.采用四参数Logistic模型能够精确地拟合芘降解过程和生物有效性变化过程(p<0.0001).土壤蔗糖酶、脲酶和多酚氧化酶对芘污染敏感,而过氧化氢酶对芘污染不敏感.实验结果揭示了河流湿地土壤芘在淹水条件下降解活跃阶段持续时间短和芘生物有效性高的特征以及土壤蔗糖酶、脲酶和多酚氧化酶活性可以作为评估芘污染影响的候选指标.     

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.     

多环芳烃在全土及其碱提残余物上的吸附行为

以菲和芘为代表性化合物,采用8种有机质含量不同的天然全土样品及其碱提残余物进行吸附实验,并利用不同吸附模型进行数据拟合,藉以探讨有机质含量对土壤吸附行为的影响.结果表明,Freundlich吸附模型的非线性指数n都小于1,显示全土和碱提残余物在多环芳烃的吸附过程中表现出非线性特征.菲和芘的吸附行为随土壤有机质含量不同而变化,碱提残余物的吸附能力强于全土,两者吸附行为的差异主要归因于土壤有机质含量和性状的区别.     

残渣吸着对消化道中土壤多环芳烃生物可给性体外测定的影响

用体外模拟方法研究了土壤中多环芳烃在消化过程中的释放,并验证了如下假设:消化过程释放出来的多环芳烃部分吸着在消化残渣相中,且该吸着可以影响多环芳烃生物可给性测定结果,研究结果表明,经消化释放出来的多环芳烃可以部分吸着在消化固相残渣中,就有机碳含量从2.87%到0.63%的四种土壤中的平均情况而言,多环芳烃残余固相上的吸着量占总可给态量的比率分别为:43.6%±14.3%(二氢苊),29.8%±24.6%(苊),43.1%±22.9%(芴),34.1%±25.8%(菲),14.0%±16.2%(蒽),25.2%±15.9%(荧蒽),33.4%±23.1%(芘),30.7%±26.6%(苯并葸)和29.1%±23.4%(芑),显然,忽略吸着现象将显著低估实际消化率,如果对吸着进行定量校正,则总多环芳烃的消化率分别从校正前的18.9%,12.2%,22.8%和33.4%增长到29.0%,29.3%,41.9%和37.6%,提升幅度在4.21%到10.1%之间.     

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.     

土壤中2,2＇,5,5＇-四氯联苯的锁定效应及其影响因素

以2,2＇,5,5＇-四氯联苯（PCB52）为典型代表,采用微波提取法研究了土壤中多氯联苯的锁定效应及其影响因素.实验表明,老化时间、土壤的有机质含量、含水率、pH值以及老化环境温度都对土壤锁定2,2＇,5,5＇-四氯联苯的效果有显著影响.2,2＇,5,5＇-四氯联苯锁定量随着老化时间的增长而增加,添加20 d后尤为显著,之后变化缓慢,趋于平衡;随着土壤有机质含量的增加而显著增加;随着土壤含水率的增大而下降,且表现出一定的线性相关性;在pH 5.5—10.5范围内,随着土壤pH值的升高而增大;在15℃到40℃范围内随着老化环境温度的升高而降低.此外,多氯联苯自身的性质也会影响土壤对其的锁定效果.     

土壤中六六六在消化道中生物可给性的体外测定

采用体外消化实验模拟了4种有机质含量不同的土壤中六六六在胃和小肠中的释放,重点验证了消化释放出来的六六六在固态消化残渣上的吸着现象以及该现象对测定消化率的影响的研究假设.结果表明,固相吸着对测定消化率有非常显著的影响,这在有机质含量偏高的土壤中尤其明显.吸着影响可以用不同液固比实验设计配合非线性拟合方法加以校正.对有机碳含量分别为0.63%、1.08%、1.60%和2.87%的4种土壤,未经校正的总六六六消化率的均值与标准差分别为(16.7±2.8)%、(11.6±2.0)%、6.9%和(26.4±1.3)%,校正后则分别达到16.7%、16.5%、16.5%和59.7%.显然,除有机质含量很低的样品,未经校正的测定结果显著低估了消化道吸收风险.     

土壤汞生物可给性的影响因素研究——基于体外模拟(in vitro)法

选取22种典型土壤,应用2种in vitro(模拟体外试验)方法——SBET法(simple bioaccessibility extraction test,生物有效性简化提取法)和PBET法(physiologically-based extraction test,生物原理提取法),定量阐明土壤性质对Hg生物可给性的影响.结果表明,SBET法中Hg的生物可给性为2.91%—35.65%,平均值为13.26%;PBET法中Hg的生物可给性为1.33%—8.69%,平均值为3.93%.所有土壤均表现为SBET法中Hg的生物可给性显著高于PBET法.pH及有机质含量是SBET法和PBET法中决定Hg生物可给性的关键影响因子,分别可以解释67.8%和81.8%的Hg生物可给性的变化;但两种方法中二者的影响程度不同:SBET法中,土壤有机质含量的影响更大,PBET法中,则是pH的影响更大.研究结果表明,污染土壤中Hg的生物可给性可以根据土壤中Hg总量、pH和有机质含量进行预测.     

玉米修复芘污染土壤的初步研究

采用60d室内盆栽试验,研究了玉米CT38(ZEAMAYSL.)对多环芳烃芘污染土壤的修复作用.结果表明,无论种植玉米土P系列、无植物对照土M系列(无植物且添加叠氮化钠的灭菌土)和对照土W系列(无植物未灭菌土)中芘的可提取浓度都随着时间的推移逐渐减少,种植玉米加快了土壤中可提取态芘浓度的下降.在芘处理浓度为10—100mg.kg-1的污染土壤中,种植玉米CT38的土壤中芘的去除率达81.9%—89.3%,分别比无植物对照土M系列和对照W系列中芘的去除率高67.5%—70.9%和26.2%—47.0%.玉米也可积累少量芘,但积累量所占芘去除量的比例不足0.3%,植物吸收不是芘去除的主要机理.种植玉米增强了土壤中脱氢酶和脲酶等酶活性,从而促进了植物-根圈微生物体系对芘的生物降解.     

土壤中结合残留态农药的生态环境效应

土壤中农药结合残留态的形成，导致其活性暂时降低，但并未从土壤中消失，在特定的环境条件下又重新释放到环境中并表现出较高的生物有效性，从而威胁农产品质量安全与环境质量。文章论述了土壤中结合残留态农药的定义、形成过程及影响因素、老化和释放过程及机制。土壤中结合残留态农药主要通过吸附过程、化学反应及物理镶嵌等作用而形成，其形成过程受农药的结构和化学特性、土壤理化性质、环境条件和农艺措施的影响。老化是化合物和土壤组分紧密结合，减少被普通提取方法提取出来的数量，降低了化合物的生物有效性。同时老化的物质在土壤环境条件改变的情况下又重新释放到土壤溶液中或进行矿化，此过程可以通过物理一化学机制或生物化学作用而发生。重新释放到环境中的结合残留态农药又表现出较高的生物有效性，可能被植物、动物或微生物所吸收，并沿食物链富集和放大或进入水体污染水产品和造成水质恶化，从而威胁人体健康。文章还分析了土壤结合残留态农药可能带来的环境问题，提出了此问题今后研究的方向。     

Evaluation of 3-hydroxy-benzo[a]pyrene levels in Nile tilapia (Oreochromis niloticus) after waterborne exposure to Benzo[a]pyrene

3-Hydroxy-benzo[a]pyrene (3-OH-BaP), a toxic compound with the ability to covalently bind with the macromolecules (proteins and DNA), is one of the major phenolic metabolites of benzo[a]pyrene (BaP). The purpose of this study was to evaluate the presence of 3-OH-BaP in the bile and plasma of Nile tilapia by HPLC with fluorescence detection, after waterborne exposure to BaP (10 and 100?µg?L^?1). Metabolites were detected in bile and plasma, and conjugates of 3-OH-BaP (glucuronide and/or sulphate conjugates) were the majority forms in both biological fluids, glucuronide 3-OH-BaP being the main metabolite in bile. Our data suggest that extrahepatic tissues as intestine or gill are important in BaP metabolism and need to be the considered sources of metabolites released into the blood. Although, low levels of 3-OH-BaP in toxic form (free form) were detected in plasma, one cannot exclude the possibility of circulating the levels leading to adverse effects.     

石灰性土壤环境中缺锌机理的探讨

作者认为石灰性土壤中锌活性较低的原因,是由于碳酸盐导致土壤pH上升,在较高pH条件下氧化铁对锌的强烈固定,造成了大量专性吸附状态的氧化铁结合态锌及部份碳酸盐结合态锌,使交换态的有效锌含量很低,同时还证明:自然的石灰性土壤中,松结有机态锌与碳酸盐结合态是活性锌的直接给源,外源加入的锌仅为松结右机态锌。此外,石灰性土壤中各主要土壤的化学组份对外源锌的固定量高伛顺序为:氧化铁>有机质>粘土矿物>碳酸盐>氧化锰:对土壤中原有锌的固定作用大小依次为:粘土矿物>氧化铁>有机质>氧化锰>碳酸盐。     

微生物对土壤和沉积物吸附多环芳烃动力学的影响

以枯草芽孢杆菌为接种微生物,研究微生物对沉积物和湿地土壤吸附菲和苯并[a]芘(BaP)吸附动力学的影响.结果表明:枯草芽孢杆菌对菲与BaP都可进行生物降解,对菲的利用率明显要大于BaP;接种微生物的土壤与沉积物对菲和BaP的吸附动力曲线与仅有微生物吸附的结果相近似,表明多环芳烃的降低主要是由于微生物的利用造成的;接种微生物后沉积物与土壤对菲的吸附量明显增大,而对BaP的吸附却降低.     

Products of laccase catalyzed reaction of 1-hydroxypyrene

The formation of residues in soils and sediments which are not readily extractable is an important fate for hydrophobic organic contaminants. Reaction of 1-hydroxypyrene, a known fungal and terrestrial invertebrate metabolite and photo-oxidation product of pyrene, with a commercially prepared laccase (an oxidoreductive enzyme) in solution provides a test system to study the fate of residues in nature. The reaction of dissolved 1-hydroxypyrene with laccase produced a distinct color change and caused a precipitate to form. At least six products were shown by HPLC analysis with photodiode array detection. The most prominent peak was composed of 1,6- and 1,8-pyrene-dione as confirmed by proton NMR analysis. LC/MS data on remaining peaks indicate that radical coupling produces acetonitrile soluble dimers and at least one trimer. Proposed structures consistent with MS and photodiode array data indicate that pyrene subunits are linked predominantly by ether bonds. Additional products, insoluble in acetonitrile, were also formed. The formation of complex products in vitro, indicates that the same mechanisms could produce bound residues in soil.     

Bestimmung der resorptionsverfügbaren PCDD/PCDF aus Kieselrot

For the estimation of intestinal absorption of polychlorianted dibenzodioxins/dibenzofurans (PCDD/F), ain-vitro model was developed in order to study PCDD/F mobilization by digestion of technogenic soils using ?Kieselrot” (red slag) as substrate and digestive juice model mixtures. Red slag samples were shaken successively with model mixtures of saliva, gastric juice, duodenal juice and bile. The solids were separated, the aqueous phase was extracted with hexane, the hexane extract analyzed for PCDD/F. Additionally, the PCDD/F-content of the red slag was determined. Extraction efficiency was tested with three different digestive juice model mixtures and also tap water for comparision. The percentage of PCDD/F transferred from the red slag sample into the digestive juice mixture was defined as absorption availability. In our experiments, a maximum absorption availability of 2 % was found.     

Reliability of solid phase microextraction in estimating bioavailability of pyrene in soil

Solid phase microextraction (SPME) coupled with gas chromatography was employed to estimate bioavailability of pyrene in soils with different properties of textures, organic matter contents (SOM) and aging periods. Experimental results indicated that biodegradation rates increased from 0.10 (sandy loam) to 0.15 (silty loam) microg g-1 hr1. By contrast, biodegradation rate decreased from 0.10(1.3% SOM) to 0.04 (7.6% SOM) microg g-1hr1. The amounts of pyrene biodegraded decreased 27% when SOM was modified from 1.3 to 7.6%, indicating that distributions of pyrene in soils at biodegradation end points were affected by the SOM. Sequestration as measured by sonication extraction had evidently occurred in aged soil samples. SPME measurements slightly overestimated the amount of pyrene degraded by indigenous and seeded microorganisms, in soils with the different properties (correlation coefficient, R2= 0.74). The present study demonstrates that the SPME method can not replace biodegradation tests commonly used for predicting bioremediation efficacy.     

Influence of inoculating earthworms on removal of pyrene in soils growing Festuca arundinacea

ABSTRACT

The aim of this study was to examine the potential of inoculating earthworms (Pheretima sp.) in order to enhance phytoremediation of polycyclic aromatic hydrocarbons (PAH) present in soils with the use of tall fescue (Festuca arundinacea). In particular, experiments with or without inoculating earthworms for removal of pyrene was investigated. Results showed that planting of F. arundinacea enhanced the removal of pyrene at initial content over 70 days approximately 54%–80% but only 12%–24% occurred in non-planted soils. After inoculating earthworms, the dissipation rates of pyrene in planted soils were increased up to 61%–86%, which was 6%–12% higher than those in corresponding soils without inoculating earthworms. Among all possible pathways, the contribution of plant--microbial interactions on removal of pyrene was predominant, either with (46%) or without inoculating earthworms (52%), is the primary mechanism of contaminant removal. Data suggest inoculating earthworms may be a feasible way for reinforcing removal of PAH in contaminated sites.     

超临界流体萃取在研究土壤和沉积物结合态残留中的应用

许多有机污染物在土壤和沉积物中形成持久稳定的结合态残留；结合态残留对土壤和沉积物的解毒过程、污染物长期分配行为、生物可用性和生物毒性都具有重要影响。为了揭示结合态残留的形成机制及其对污染物环境行为和毒理学参数的影响，从土壤或沉积物中提取出不同结合状态的有机污染物就显得非常重要。超临界流体萃取(SFE)可以实现选择性萃取，从而得到有关污染物一基体间相互作用的信息。文章介绍了SFE应用类型、超临界流体种类以及影响SFE萃取率的因素，对SFE模拟有机污染物长期吸附／解吸行为和生物可用性研究进行了论述，并认为SFE势必发展成为土壤或沉积物中结合态残留形成机理研究、土壤修复和生态风险评价的一种强有力的技术。