土壤中多环芳烃的SPMD辅助解吸行为研究

为了开发一种表征土壤中憎水性有机污染物解吸及生物有效性的新方法,建立了半透膜被动采样装置（SPMD）研究土壤中有机污染物解吸行为的方法,利用SPMD分析了多环芳烃菲、芘和苯并［a］芘在3种不同性质土壤中的辅助解吸行为.结果表明,SPMD是一种很好地表征土壤中憎水性有机污染物解吸及生物有效性的手段. SPMD辅助解吸多环芳烃的效率与土壤有机质及多环芳烃性质有关.随着土壤有机质含量的降低,土壤中菲和芘的SPMD解吸率逐渐升高,对于10 mg/kg染毒水平,当土壤有机质含量由18.68%降低到0.3%时,2种化合物的解吸率分别由56.45%和48.28%上升到接近100%;但是对于苯并［a］芘,粘土表现出明显的滞留能力,在有机质含量（0.3%）很低、粘土含量（39.05%）较高的3号土壤中,苯并［a］芘的解吸率仅有66.97%.不同多环芳烃SPMD辅助解吸率差别很大,随着土壤有机质含量的降低,以及污染物浓度的提高,菲和芘的解吸差异逐渐缩小,而苯并［a］芘与上述2种多环芳烃的差异很大,主要是由于苯并［a］芘具有高度亲脂性,并且分子较大,造成其容易滞留在粘土的微孔及有机质的致密结构中.     

鼠李糖脂与β-环糊精复合提取预测污染土壤中PAHs的生物有效性

以添加3种典型多环芳烃(PAHs)菲(Phe)、芘(Pyr)、苯并[a]芘(Ba P)的模拟污染土壤(海南红壤)为对象,研究了鼠李糖脂(RL)与β-环糊精(HPCD)复合提取预测污染土壤中PAHs的生物有效性的可行性.结果表明,当RL浓度大于临界胶束浓度时,由于其胶束增溶作用,PAHs的表观溶解度随RL浓度增加而增加,促使更多的PAHs从土壤固相解吸进入土壤溶液中.通过HPCD/RL复合提取土壤中的PAHs的含量与蚯蚓体内吸收的PAHs的量进行相关性分析,发现两者之间存在显著的正相关关系.但是PAHs蚯蚓吸收量是HPCD单独提取量的2.04倍,是HPCD/RL提取量的1.15倍.结果表明,HPCD/RL比HPCD对PAHs提取更能接近蚯蚓富集.因此,RL的添加在一定程度上增加了HPCD对污染土壤中PAHs生物有效性的预测效果,HPCD/RL复合提取法可以作为一种相对快捷可靠的预测PAHs生物有效性的方法.本研究为复合提取在有机污染物生物有效性评价方面提供一个新的方向,也为有机污染物的风险评估和生物修复提供了一定的技术支持.     

蚯蚓辅助微生物修复芘污染土壤

通过微宇宙实验,研究了蚯蚓对不同土壤中芘的微生物降解率的影响及蚯蚓对芘的富集率.结果表明,有机质较高土壤中芘的微生物降解率和蚯蚓富集率都低于有机质低的土壤,而老化作用降低了芘的生物有效性.无论在新鲜染毒还是老化的土壤中.蚯蚓均可提高土壤中芘的去除率和微生物降解率.在新鲜染毒的红壤和潮土中,蚯蚓可使芘的去除率由41.78%和27.02%分别提高到89.24%和57.53%,其中分别有51.48%和41.63%是蚯蚓促进的微生物降解作用引起的,37.76%和15.90%归因于蚯蚓富集作用.而在老化的红壤和潮土中,蚯蚓可使芘的去除率由36.53%和20.50%分别提高到91.93%和45.46%,其中分别有54.43%和32.83%是蚯蚓促进的微生物降解作用引起的,37.50%和12.63%归因于蚯蚓富集作用.     

Tenax提取预测老化土壤中多环芳烃的生物有效性

利用聚2,6-二苯基对苯醚(poly(2,6-diphenyl-p-phenylene oxide),商品名Tenax-TA)提取来自9个老化农田土壤中的多环芳烃(PAHs),并应用Tenax-TA评价老化土壤中PAHs对赤子爱胜蚓(Eisenia Fetida)的生物有效性.结果表明,多年老化土壤中污染物的主要组成为4环以上的PAHs;蚯蚓较易富集低环PAHs,对高环PAHs富集能力较差;400h Tenax连续提取实验得出快速、慢速和极慢速吸附速率常数数量级分别为:10-1~10-2、10-2~10-3、10-4~10-6;而快速、慢速和极慢速解吸比率分别为0.02~0.27、0.01~0.33和0.40~0.95.Tenax 6h单点提取PAHs的量与蚯蚓体内PAHs富集量显著相关,表明6h Tenax对多年老化土壤中PAHs的提取量可以用来作为其生物有效性的评价方法.     

温和溶剂提取预测土壤中多环芳烃的生物有效性

利用正丁醇和羟丙基-β-环糊精（hydroxypropyl-β-cyclodextrin,HPCD）提取来自9个农田土壤中的多环芳烃（polycyclicaromatic hydrocarbons,PAHs）,并应用于评价场地多年老化土壤中PAHs对赤子爱胜蚯蚓（Eisenia fetida）的生物有效性.结果表明,对...     

城市污泥对通菜-水稻土中有机污染物的累积效应

在水稻土上施用城市污泥及化肥盆栽通菜,应用GC/MS对通菜植株和土壤中的邻苯二甲酸酯(PAEs)和多环芳烃(PAHs)等7类43有机污染物进行系统分析,探讨通菜植株和土壤中其累积效应.结果表明,通菜植株中检出邻苯二甲酸酯、多环芳烃、氯苯类、硝基苯类、醚类和卤代烃类共6类28种化合物(胺类未检出),土壤中检出上述7类33种化合物,均以PAEs和PAHs为主,其总含量是其他类污染物的几倍或数十倍.不同处理的通菜和土壤中各类有机污染物的含量差别较大,均以个别或少数污染物为主.施用城市污泥增加了植株和土壤中PAEs和PAHs等污染物的含量.强致癌性化合物苯并(a)芘在通菜中被检出,在部分土壤中的含量超过加拿大土壤质量控制标准(1.0mg/kg).除佛山污泥处理的通菜对氯苯类和醚类的生物浓缩系数(BCF)大于1外,其余均小于1.0.     

太湖地区3种水稻土不同温度培养中有机碳库变化及其对升温的响应

全球变暖下土壤有机碳储存的变化是土壤与全球变化研究的热点问题.本研究选择了3种太湖地区代表性水稻土的表层土壤,分别进行20℃和25℃的室内恒温培养,监测培养过程中总有机碳、溶解性有机碳和微生物量碳的变化动态,试图了解这些土壤的有机碳分解过程对全球变暖的响应特点.结果表明,这些土壤培养中总有机碳变化可以用一级衰变动力学方程或对数衰减方程描述,但动力学特征依培养温度的不同而异.升温大大促进了铁渗水耕人为土和潜育水耕人为土中有机碳的分解与呼吸损失,而铁聚水耕人为土没有显著变化.供试土壤总有机碳损失的Q₁₀系数分别为:潜育水耕人为土(11.1～14.1)＞铁渗水耕人为土(4.4～6.4)＞铁聚水耕人为土(0.63～0.73).这一方面说明温度敏感性在同一地带的不同土壤间的差异超过文献上报道的不同气候带的差异,但另一方面揭示了水稻土可能是一类对全球升温敏感响应的人为土.溶解性有机碳和微生物量的碳的变化还提示不同温度培养下水稻土微生物群落结构可能改变,因而影响到土壤有机碳库的生物有效性在温度条件下的变化.可以认为,土壤升温下有机碳的变化不但与土壤有机碳的性质有关,而且与土壤性质控制下的生物条件的改变有关.故土壤升温下有机碳的损失不仅仅是温度对分解过程的反应速度的影响.当然,对于不同土壤间的这种差异还需从有机碳-土壤环境-土壤生物的相互关系上做进一步的工作.     

安徽庐江潜在富硒土壤硒生物有效性及其影响因素

为研究潜在富硒土壤硒生物有效性,采集安徽庐江潜在富硒地区64组水稻及对应根系土壤样品,分析土壤理化性质、土壤养分、全硒、不同形态硒及大米硒含量,采用线性回归法探究土壤硒生物有效性的影响因素.结果表明,大米硒含量（记作Se_rice,下同）为0.037~0.120 mg/kg,土壤全硒含量（记作Se_tot,下同）为0.260~1.177 mg/kg,土壤硒以腐殖酸态硒（15.5%~44.7%）、强有机态硒（12.5%~53.3%）和残渣态硒（8.1%~68.5%）为主.土壤有效硫、有效磷通过提高强有机态、腐殖酸态和浸提性硒含量并促进水稻籽实（大米）对硒的吸收,而土壤阳离子交换量（cation exchange capacity,CEC）、速效钾、全铁和全锰通过降低水稻生物可利用态硒含量（包括水溶态、腐殖酸态、强有机态和浸提性硒）抑制水稻籽实（大米）对硒的吸收.Se_tot与Se_rice显著正相关（R=0.616,P < 0.01）,非残渣态硒含量与有机质含量之比（记作NRE-Se/OM）与Se_rice相关性最强（R=0.774,P < 0.01）.土壤NRE-Se/OM、有效硫、有效铁、全锰构建的多元逐步线性对数回归模型可解释水稻籽实（大米）吸收硒的76.0%的方差.因此引入变量NRE-Se/OM,并结合土壤有效硫、有效铁和全锰能有效评价和预测研究区土壤硒生物有效性.      

化学提取法表征污染土壤中PAHs老化规律和蚯蚓富集特征

以添加3种典型多环芳烃(菲、芘、苯并[a]芘)的模拟污染土壤(黄壤和红壤)为对象,研究了PAHs的4种化学提取量即:ASE耗竭性提取总量、Tenax-TA树脂提取量、羟丙基-β-环糊精(HPCD)提取量和正丁醇提取量随老化时间的变化规律.结果表明,在0~60 d老化时间范围内,PAHs耗竭性提取总量在前30 d随时间的延长而降低,后30 d降低趋势不明显,含量基本稳定;PAHs的Tenax、HPCD、正丁醇提取量在0~60 d老化时间范围内,随老化时间的延长而持续降低.实验进一步研究了PAHs的蚯蚓蓄积量(赤子爱胜蚓Eisenia fetida)与4种化学法提取量的相关关系.结果显示,ASE耗竭性提取总量高估了土壤中PAHs的存在风险,并且与蚯蚓富集量没有显著的相关性(R~2为0.44~0.56),因此不能用耗竭性提取总量来评估污染土壤PAHs的生物有效性;而3种非耗竭性提取量与蚯蚓富集量呈现出较好的线性关系,其中HPCD提取法(R~2为0.94~0.99)较Tenax提取(R~2为0.62~0.87)和正丁醇提取(R~2为0.69~0.94)更优.表明可以将HPCD提取法作为预测污染土壤中PAHs生物有效性的一种较为理想的方法.     

难降解多环芳烃污染土壤的机械力化学修复

利用机械力化学法修复多环芳烃污染土壤,以四环芳烃芘为代表污染物,研究了球磨时间和球磨转速对土壤中芘去除率的影响。当球磨时间为6 h,球磨速度为500 r/min时,土壤中芘去除率为93.78%。利用SiO₂作为模拟土壤,通过对球磨前后模拟土壤的GC-MS、红外光谱和拉曼光谱分析,探索芘的降解途径和机理。机械力化学修复过程中,芘的苯环被破坏,部分中间产物为环数较少的多环芳烃(PAHs)、碳链较短的烷烃,还有部分被碳化成石墨和不定形碳。利用机械力化学法对实际污染土壤进行修复,修复后土壤中芘和荧蒽浓度分别为21.45,35.68 mg/kg。机械力化学法修复多环芳烃污染土壤具有可行性和广泛的应用前景。     

Bioaccumulation of hexachlorobenzene in Eisenia foetida at di erent aging stages

The impacts of contact time on the extractability, the availability of hexachlorobenzene (HCB) in di erent soils (paddy soil, red soil, and fluvo-aquic soil) and bioaccumulation in earthworm Eisenia foetida were investigated under controlled conditions in laboratory. Results indicated that the aging rate of HCB displaying a biphasic character in di erent soils: a rapid aging in the first 60 d followed by a slow aging in the next 120 d incubation time. Moreover, most of extractable HCB (about 90%) decline occurred in the first 60 d after HCB was spiked into the soils. The aging rate of HCB in the paddy soil was higher than that in the fluvo-aquic soil or the red soil. The amount of HCB accumulated in the earthworms and its accumulative ability, expressed as a bioaccumulation factor (BAF), declined as the aging time increased from 1 to 180 d. Although the extractable HCB decreased with increasing residence time in soil, much of HCB could still be accumulated by earthworms (457.6–984.3 ng/g) through bioaccumulation, which poses a potential risk to soil ecological safety.     

Bioaccumulation of hexachlorobenzene in Eisenia foetida at different aging stages

The impacts of contact time on the extractability, the availability of hexachlorobenzene (HCB) in different soils (paddy soil, red soil, and fluvo-aquic soil) and bioaccurnulation in earthworm Eisenia foetida were investigated under controlled conditions in laboratory. Results indicated that the aging rate of HCB displaying a biphasic character in different soils: a rapid aging in the first 60 d followed by a slow aging in the next 120 d incubation time. Moreover, most of extractable HCB (about 90%) decline occurred in the first 60 d after HCB was spiked into the soils. The aging rate of HCB in the paddy soil was higher than that in the fluvo-aquic soil or the red soil. The amount of HCB accumulated in the earthworms and its accumulative ability, expressed as a bioaccumulation factor (BAF), declined as the aging time increased from 1 to 180 d. Although the extractable HCB decreased with increasing residence time in soil, much of HCB could still be accumulated by earthworms (457.6-984.3 ng/g) through bioaccumulation, which poses a potential risk to soil ecological safety.     

Bioaccumulation of hexachlorobenzene in Eisenia foetida at dierent aging stages

The impacts of contact time on the extractability, the availability of hexachlorobenzene (HCB) in dierent soils (paddy soil, red soil, and uvo-aquic soil) and bioaccumulation in earthworm Eisenia foetida were investigated under controlled conditions in laboratory. Results indicated that the aging rate of HCB displaying a biphasic character in dierent soils: a rapid aging in the first 60 d followed by a slow aging in the next 120 d incubation time. Moreover, most of extractable HCB (about 90%) decline occurr...     

芘在土壤不同粒径组分中的形态分布

以芘为PAHs代表物,采用土壤粒径分级和PAHs连续提取方法,研究了老化4周污染黄棕壤中芘在不同粒径组分中的形态分布.结果表明,供试土壤中芘主要以有机溶剂提取态和可脱附态存在,结合态残留量所占比例甚小;细砂粒、粉粒、粗黏粒和细黏粒中芘残留占原土总残留的比例分别为6.00%、4.66%、34.68%和40.88%.各粒径组分中各形态芘含量大小顺序为有机溶剂提取态>可脱附态>结合态,有机溶剂提取态和可脱附态是各粒径组分中芘残留的主要存在形态(占比98.82%以上),芘结合态残留量占比<1.18%.土壤中黏粒(包括细黏粒和粗黏粒)是芘可脱附态、有机溶剂提取态、结合态和可提取态残留储存的主要粒径组分.     

土壤中不同有机质对菲的吸附行为及生物可利用性的影响

为了研究不同有机质对持久性有机污染物(POPs)的吸附行为及生物可利用性的影响,从黑龙江省未被多环芳烃(PAHs)污染的农业表层土壤中提取了矿质结合态胡敏酸(MHA)、矿质结合态胡敏素(MHU),通过绘制吸附动力学曲线和吸附等温线,研究了MHA、MHU及全上本身对菲的吸附特性,并通过改变老化时间和吸附剂质量,研究了不同...     

Aging effect on the mobility and bioavailability of copper in soil

Aging effect on the mobility and bioavailability of copper (Cu) was investigated using a spiked soil with different incubation periods from 3 to 56 d. Wheat was planted and earthworm was cultured separately in the incubated soils. The mobility of Cu in soil was evaluated by a chemical fractionation scheme and the toxicity and bioavailability were assessed by measuring the biomass and Cu concentration in tissues. Results showed that aging had a significant effect on Cu fraction distribution, of which Cu tended to incorporate from the exchangeable into more stable fractions such as the reducible and oxidisable fractions. However, aging had little effect on Cu bioavailability to wheat and earthworms. Comparing the soil being incubated for 3 d and 56 d, Cu concentration in wheat roots decreased from 14.5 to 12.8 mg/kg, and no significant changes in Cu concentration were observed in both wheat shoots and earthworms. The Cu concentration was around 2.0 and 50 mg/kg for wheat shoots and earthworms, respectively, irrespective of soil incubation time. The CaCl2-extractable Cu had a linear relationship with Cu concentration in wheat roots (R2 = 0.65, P < 0.05), but no linear relationship can be found for wheat shoots and earthworms. Biological control may be more crucial for Cu accumulation in organism than the changes in soil Cu fraction caused by aging.     

生物质炭对土壤中氯苯类物质生物有效性的影响及评价方法

通过室内培养实验,设定对照和添加1%小麦秸秆生物质炭处理,研究生物质炭对土壤中氯苯类物质老化残留的影响,并通过丁醇、HPCD和Tenax这3种化学提取方法以及蚯蚓富集实验评价土壤中氯苯类物质生物有效性的变化.老化4个月后,对照处理中六氯苯、五氯苯和1,2,4,5-四氯苯的残留率分别为29.87%、18.02%、5.16%,而添加1%生物质炭处理中六氯苯、五氯苯和1,2,4,5-四氯苯的残留率分别为68.25%、61.32%和58.02%,表明添加生物质炭能够抑制氯苯的消减.丁醇、HPCD和Tenax提取和蚯蚓富集实验结果表明,添加生物质炭显著降低土壤中氯苯的生物有效性(P<0.05),并随老化时间延长,降低效果更为显著.不同提取剂对氯苯的提取效率不同,丁醇和Tenax对氯苯的提取率为六氯苯>五氯苯>1,2,4,5-四氯苯,而HPCD对氯苯的提取率为1,2,4,5-四氯苯>五氯苯>六氯苯.添加生物质炭可显著降低蚯蚓对氯苯的生物富集因子(P<0.05).本研究表明,生物质炭能降低土壤中有机污染物的生物有效性,但高污染残留存在潜在的环境风险.     

LAS对土壤环境理化性状和生物活性的影响

以太湖地区黄泥土为例 ,通过土壤物理性质测定、毒性物质吸附实验以及实验室微生物培养 ,研究了不同浓度LAS对土壤环境理化性质和微生物活性的影响 .表明LAS显著影响土壤溶液性质 ,降低土壤环境对苯酚的吸附量 ,但对重金属离子的吸附无明显效应 ;土壤硝化作用和氨化作用对LAS十分敏感 ,反硝化作用受到一定程度的促进 ;土壤中细菌受到LAS的刺激 ,而真菌受到抑制 ;土壤呼吸活性在培养前期随LAS浓度表现增强 ,但在 >5mg/L浓度下 ,一周后均表现出抑制 .本研究表明 ,土壤中存在对LAS耐受的微生物群落 .土壤对LAS污染的环境效应与土壤类型和性质有关 ,尚需进一步研究 .     

Sorption of pyrene on two paddy soils and their particle-size fractions

In the present study, the sorption of pyrene on two kinds of bulk paddy soils, Gleyic Stagnic Anthrosols, and Ferric accumulic Stagnic Anthrosols as well as their particle-size fractions was investigated. The sorption isotherms fitted well with Freundlich equation. For both soils, the clay fraction（ 〈 2μm） and coarse sand fraction（2000-250μm） had higher sorption capacity than fine sand fraction（250-20 μm） and silt fraction（20-2 μm）. The IogKoc values obtained of each soil and its particle-size fractions were similar, proving that SOM content was a key factor affecting pyrene sorption. The Kd values showed a significant correlation with contents of dithionite-extractable Fe in both paddy soils and a good relationship with CEC in Gleyic Stagnic Anthrosols, indicating possible effects of surface properties of particle-size fractions on the sorption of pyrene.