生物质炭-过氧化氢联合修复对火电厂土壤性质与小白菜生长的影响

本文建立了一种利用生物质炭并结合过氧化氢对火电厂多环芳烃(PAHs)污染土壤的修复方法.采集诸城火电厂多环芳烃污染土壤为研究对象,采用盆栽试验的方法,研究了不同梯度生物质炭与过氧化氢配合施用修复多环芳烃污染土壤,对小白菜生长指标及土壤多环芳烃含量的变化.结果表明,合理施用生物质炭配施过氧化氢能促进小白菜生长,有效降低土壤和小白菜中多环芳烃含量.与T1(不施生物质炭)对比,生物炭处理的小白菜生物量增加8%—15%,叶绿素SPAD值增加25%—50%,荧光参数和光谱反射率有一定提高,小白菜和土壤多环芳烃含量显著减少.同时,使污染酸化土壤pH值提高了0.2—0.6个单位,土壤有机质含量提高了9.5%—45.6%,碱解氮、速效磷与速效钾等养分有一定量的增加.其中,T7(0.5‰H_2O_2+2‰生物质炭)处理修复效果最好,供试蔬菜和土壤中多环芳烃去除率分别达到了69.6%和58.8%.其次是T3(2‰生物质炭)处理,供试蔬菜和土壤中多环芳烃去除率分别达到了42.9%和54.6%,也具有较好的去除效果.因此,可推荐在修复实践中参考应用.     

芘对玉米根系分泌氨基酸的影响

植物根系释放分泌物是根际修复土壤多环芳烃污染的重要机制之一,但对于多环芳烃污染下根系分泌物的研究很少.以玉米Zea mays L.为供试材料,通过土培培养试验方式研究了在多环芳烃芘处理下,玉米根系分泌氨基酸的变化.结果表明,种植玉米2 1 d后,低质量分数芘(75 mg·kg-1)处理和高质量分数芘(600 mg·kg-1)处理种植玉米土壤芘的去除率分别为36.0%和28.2%.氨基酸分泌总量随着芘胁迫的加强显著增多,低质量分数芘处理和高质量分数芘处理下氨基酸分泌总量分别是无芘胁迫处理下的1.25倍和5.12倍.不同芘质量分数处理下玉米根系分泌的氨基酸的种类和数量的变化情况不相同.     

长春城郊蔬菜地土壤中多环芳烃的含量与分布特征

以长春城市郊区菜地土壤为研究对象,采用GC-FID法对该地区土壤中多环芳烃含量进行分析测定,长春城郊菜地土壤中平均含量苯并(a)芘蒽菲萘.该地区土壤中萘,蒽的含量处于尚清洁水平;部分区域土壤中苯并(a)芘和菲的含量处于轻度污染水平.     

芘污染土壤的根瘤菌-植物修复效应研究

土壤多环芳烃(PAHs)的污染已经成为了全球性的热点问题,微生物-植物联合修复技术是解决土壤有机污染的一种低耗高效的新型修复技术。以往作为目标污染物,绿豆根瘤菌(Rhizobium leguminosarum),紫花苜宿根瘤菌(Rhizobium meliloti)为供试微生物,选用绿豆(Vigna radiata L.)、紫花苜蓿(Medicago sativa L.),黑麦草(Lolium perenne L.)和花生(Arachis hypogaea L.)作为修复植物。采用盆栽实验,研究在100 mg·kg-1污染条件下,接种根瘤菌对植物修复法污染土壤效果的影响。结果表明:培养60d后,4种植物均提高了芘污染土壤的pH,并提高了土壤脱氢酶的活性,其中种植绿豆的效果最好,其次为花生。此外,4种植物均提高了土壤中芘的去除率,提高幅度依次为绿豆(33.70%)花生(21.63%)黑麦草(10.55%)苜蓿(7.72%)。接种根瘤菌后发现,绿豆和花生根瘤数显著高于对照组,苜蓿与根瘤菌没有结合,而黑麦草则不和根瘤菌共生。根瘤菌对土壤中pH有一定的提高作用,但效果不显著。此外,根瘤菌提高了绿豆、花生和紫花苜蓿的生物量以及绿豆和花生处理组土壤的脱氢酶活性。并提高了绿豆和花生对土壤中芘的去除率,分别为4.10%和2.02%。研究表明:种植绿豆对土壤芘的去除率最高(94.63%),根瘤菌能与其根系结合良好,强化了绿豆修复芘污染土壤的能力,结果可为微生物-植物修复芘污染土壤提供新的参考。     

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.     

混种模式对土壤中PAHs污染的强化修复作用

以菲、芘为多环芳烃(PAHs)的代表,选择多环芳烃初始浓度在20.05~322.06 mg·kg-1的污染土壤为研究对象,采用温室盆栽的方法,选用三叶草(Trifolium repens)单种、紫花苜蓿(Medicago sativa)单种和三叶草-紫花苜蓿混种3种模式,通过测定实验70 d后土壤中PAHs的浓度,研究不同种植模式下植物对PAHs污染的去除效果和修复机制。结果表明,(1)在实验浓度范围内,在三叶草和紫花苜蓿混种模式下,土壤中PAHs的去除率最高,明显高于单种模式。在70 d的实验期间,约有75.47%的菲和68.28%的芘被降解,而单种模式下三叶草和紫花苜蓿对菲的降解率分别为31.79%和64.03%,对芘的降解率分别为27.97%和52.18%。(2)相同污染水平下,茎叶部PAHs的含量低于根部,菲的含量低于芘,混种模式下植物体内PAHs的含量低于单种模式下的含量。(3)生物作用对土壤中菲的去除率在三叶草、紫花苜蓿组和混合组中分别为26.69%、58.98%和69.84%,对芘的去除率分别为25.29%、48.98%和65.86%,明显高于非生物作用。在生物作用中植物-微生物的联合效应是最主要的,在三叶草组、紫花苜蓿组和混合组中对菲、芘的去除率分别为6.95%、34.85%、42.95%和6.3%、26.78%、38.98%。微生物作用在各种模式下相同,混种模式下,植物作用、植物-微生物联合效应均高于单种模式。说明借助多物种混合种植模式对改善PAHs污染土壤修复效果、减少植物体内PAHs积累和缓解生态风险具有可行性。     

钢铁工业区周边农业土壤中多环芳烃(PAHs)残留及评价

对某大型矿业企业周边农业土壤中多环芳烃(PAHs)残留量进行了调查。结果表明,PAHs总残留量范围为312. 2~27 580. 9ng·g-1,且以4环以上多环芳烃组分为主。所有土样中均检出PAHs,单一污染物以芘、艹屈、荧蒽、苯并[a]芘、蒽、菲、苯并[a]蒽、苯并[k]荧蒽、茚并[1,2,3 cd]芘、苯并[g,h,i]苝为主。PAHs残留量与有机质含量相关性较好。不同样区土壤PAHs残留量受常年风向影响明显。以加拿大农业区域土壤PAHs的治理标准值为指标,用内梅罗综合指数法进行评价表明,研究区农业土壤达重污染水平的占37%,中度污染的占19%,轻污染的占25%,另有13%的采样点污染程度处于警戒限,仅有6%的采样点尚处于安全级。     

基于健康风险的土壤修复目标研究程序与方法——以多环芳烃污染土壤再利用工程为例

提出了基于人体健康风险的土壤修复目标的制定方法和程序,并以上海市某重大工程多环芳烃污染土壤处理后再利用工程为例,模拟了多环芳烃在处置场地上的多介质迁移途径及人体暴露场景。模拟结果显示,填埋场污染土壤苯并(a)芘(该污染物毒性因子高,毒性强,致癌风险相对较大)经口摄入和皮肤接触途径最大致癌暴露量分别为1.89×10-6和0.93×10-6mg.kg-1.d-1,人体最大致癌风险水平分别为1.38×10-5和6.79×10-6,超出了中国规定的单致癌污染物的可接受风险水平(≤10-6)。苯并(a)芘呼吸吸入途径最大致癌暴露量为7.79×10-10mg.m-3,人体最大致癌风险水平为6.86×10-10。基于场地的特征条件和参数,以保护人体健康为目的,确定了再利用作为填埋场中层覆土的土壤中5种多环芳烃污染物的修复目标限值(w,mg.kg-1)分别为:苯并(a)芘,0.994;二苯并(a,h)蒽,0.995;苯并(a)蒽,9.95;苯并(b)荧蒽,9.95;苯并(k)荧蒽,99.5。     

呼和浩特市冬季PM_(10)中多环芳烃的污染特征及来源解析

2013年12月在呼和浩特市主城区9个环境空气监测点位同步采集PM_(10)样品,对PM_(10)浓度和16种多环芳烃的浓度、污染特征进行了分析,使用特征比值和主成分分析对多环芳烃来源进行了解析.9个监测点位的PM_(10)浓度介于23.5—322μg·m-3之间,16种多环芳烃总量介于5.34—850 ng·m-3之间.荧蒽、芘、苯并[a]蒽、、苯并[b]荧蒽、苯并[a]芘、苯并[g,h,i]苝和茚并[1,2,3-cd]芘等多环芳烃单体浓度较高,这8种多环芳烃占多环芳烃总浓度的80.4%.主成分分析所获得污染源结果和特征比值法定性判断出的污染源结果一致,燃烧源、机动车尾气源和石油源为主要污染源,分别贡献61.3%、16.0%和10.4%.     

应用物种敏感性分布评估多环芳烃对淡水生物的生态风险（Assessing Ecological Risks of Polycyclic Aromatic Hydrocarbons（PAHs）to Freshwater Organisms by Species Sensitivity Distributions）

阐述了利用物种敏感性分布进行生态风险评价的原理与方法,构建了淡水生物对8种常见多环芳烃(蒽、芘、苯并[a]芘、荧蒽、菲、芴、苊、萘)的物种敏感性分布;在此基础上,计算了这8种多环芳烃对不同类别生物的HC5(Hazardous Concentration for5%of the species)阈值,预测了不同浓度多环芳烃对生物的潜在影响比例PAF(Potentialaffected fraction),比较了不同类别生物对多环芳烃的敏感性,以及多环芳烃对淡水生物的生态风险,并对以红枫湖、黄河、白洋淀为代表的中国典型水体中的多环芳烃进行了联合生态风险评价.结果表明:1)当污染物浓度达到10μg·L-1时,半数多环芳烃的风险超过了5%的阈值;当浓度上升到100μg·L-1时,只有萘和苊没有显著生态风险.2)对于芴和荧蒽,无脊椎动物更为敏感;而对于萘,则脊椎动物更敏感.3)通过HC5值比较和SSD曲线图比较,可得出污染物对所有物种的生态风险大小依次为:蒽>芘>苯并[a]芘>荧蒽>菲>芴>苊>萘;对脊椎动物风险大小为:荧蒽>苊>萘;对无脊椎动物:蒽>芘>荧蒽>菲>芴>苊>萘.4)多环芳烃在红枫湖、黄河、小白洋淀的生态风险均较低,急性联合msPAF(multisubstance PAF)值小于1%.     

Removal of high concentrations of polycyclic aromatic hydrocarbons from contaminated soil by biodiesel

Solubilizing experiments were carried out to evaluate the ability of biodiesel to remove polycyclic aromatic hydrocarbons (PAHs) from highly contaminated manufactured gas plant (MGP) and PAHs spiked soils with hydroxypropyl-β-cyclodextrin (HPCD) and tween 80 as comparisons. Biodiesel displayed the highest solubilities of phenanthrene (420.7 mg·L^-1), pyrene (541.0 mg·L^-1), and benzo(a)pyrene (436.3 mg·L^-1). These corresponded to several fold increases relative to 10% HPCD and tween 80. Biodiesel showed a good efficiency for PAH removal from the spiked and MGP soils for both low molecular weight and high molecular weight PAHs at high concentrations. Biodiesel was the best agent for PAH removal from the spiked soils as compared with HPCD and tween 80; as over 77.9% of individual PAH were removed by biodiesel. Tween 80 also showed comparable capability with biodiesel for PAH solubilization at a concentration of 10% for the spiked soils. Biodiesel solubilized a wider range of PAHs as compared to HPCD and tween 80 for the MPG soils. At PAH concentrations of 229.6 and 996.9 mg·kg^-1, biodiesel showed obvious advantage over the 10% HPCD and tween 80, because it removed higher than 80% of total PAH. In this study, a significant difference between PAH removals from the spiked and field MGP soils was observed; PAH removals from the MGP soil by HPCD and tween 80 were much lower than those from the spiked soil. These results demonstrate that the potential for utilizing biodiesel for remediation of highly PAH-contaminated soil has been established.     

Soil washing of As-contaminated stream sediments in the vicinity of an abandoned mine in Korea

A soil washing process was applied to remediate arsenic (As)-contaminated stream sediments around an abandoned mine in Goro, Korea. Laboratory scale soil washing experiments for As-contaminated stream sediments were performed under various washing conditions in order to maximize As removal efficiency. Stream sediments were taken from two sites (S1 and S5) along the main stream connected to an abandoned mine. Stream sediments at the two sites were divided into two groups (≥0.35 and <0.35 mm in diameter), giving four types of sediments, which were thereupon used for soil washing experiments. The results of soil washing experiments involving various pH conditions suggested that As removal efficiency is very high in both strongly acidic and basic solutions (pH 1 and 13), regardless of sediment type. Removal efficiencies for fine sediments from S1 and S5 were >95% after 1 h of washing with 0.2 M citric acid (C₆H₈O₇). When using 0.2 M citric acid mixed with 0.1 M potassium phosphate (KH₂PO₄), the As removal efficiency increased to 100%. When recycled washing solution was applied, As removal efficiency was maintained at a level greater than 70%, even after eight recycling events. This suggests that the recycling of washing solution could be successfully applied as a means of decreasing the cost of the washing process. Results from the experiments suggest that soil washing is a potentially useful process for the remediation of As-contaminated stream sediments around abandoned mines.     

Phylogenetic analysis of hyperaccumulator plant species for heavy metals and polycyclic aromatic hydrocarbons

Increasing concentration of heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) in the soil may impose a serious threat to living organisms due to their toxicity and the ability to accumulate in plant tissues. The present review focuses on the phylogenetic relationships, sources, biotransformation and accumulation potential of hyperaccumulators for the priority HMs and PAHs. This review provides an opportunity to reveal the role of hyperaccumulators in removal of HMs and PAHs from soils, to understand the relationships between pollutants and their influence on the environment and to find potential plant species for soil remediation. The phylogenetic analysis results showed that the hyperaccumulators of some chemicals (Co, Cu, Mn, Ni, Zn, Cd) are clustered on the evolutionary tree and that the ability to hyperaccumulate different pollutants can be correlated either positively (Cd–Zn, Pb–Zn, Co–Cu, Cd–Pb) or negatively (Cu–PAHs, Co–Cd, Co–PAHs, Ni–PAHs, Cu–Ni, Mn–PAHs). Further research needs to be extended on the focus of commercializing the techniques including the native hyperaccumulators to remediate the highly contaminated soils.

     

固定化毛霉对工业和农田污染土壤中多环芳烃的降解和生物有效性评价

为了探讨微生物修复不同类型多环芳烃污染土壤的可行性,应用固定化毛霉对多环芳烃污染工业土壤及农田土壤进行微生物修复,用羟丙基-β-环糊精(HPCD)提取模拟评价多环芳烃的微生物可利用性,并分析多环芳烃微生物降解和生物可利用性的相关关系.焦化厂污染土壤中多环芳烃的30 d降解率为77.6%,沈抚灌区污染土壤中多环芳烃的30 d降解率为54.2%,焦化厂土壤和污灌区农田土壤中多环芳烃降解差异明显.焦化厂土壤和污灌区土壤中多环芳烃的30 d降解量和多环芳烃的环糊精可提取量具有相关性,各环数多环芳烃的环糊精可提取量变化解释了焦化厂和污灌区土壤中多环芳烃降解的差异机制,说明可用环糊精提取量预测微生物降解土壤多环芳烃的情况.     

Synergistic degradation of pyrene and volatilization of arsenic by cocultures of bacteria and a fungus

The combination of two bacteria (Bacillus sp. PY1 and Sphingomonas sp. PY2) and a fungus (Fusarium sp. PY3), isolated from contaminated soils near a coking plant, were investigated with respect to their capability to degrade pyrene and volatilize arsenic. The results showed that all strains could use pyrene and arsenic as carbon and energy sources in a basal salts medium (BSM), with the combined potential to degrade pyrene and volatilize arsenic. Bacillus sp. PY1, Sphingomonas sp. PY2 and Fusarium sp. PY3 were isolated from the consortium and were shown to degrade pyrene and volatilize arsenic independently and in combination. Fungal-bacterial coculture has shown that the most effective removal of pyrene was 96.0% and volatilized arsenic was 84.1% after incubation in liquid medium after 9 days culture, while bioremediation ability was 87.2% in contaminated soil with 100 mg·kg^-1 pyrene. The highest level of arsenic volatilization amounted to 13.9% of the initial As concentration in contaminated soil after 63 days. Therefore, a synergistic degradation system is the most effective approach to degrade pyrene and remove arsenic in contaminated soil. These findings highlight the role of these strains in the bioremediation of environments contaminated with pyrene and arsenic.     

典型污水处理厂对多环芳烃及其衍生物的去除及再生水健康风险研究

多环芳烃(PAHs)在水环境中可以通过化学或微生物作用转化成其衍生物(SPAHs),而SPAHs可能具有更强的毒性和"三致性"从而危害人体健康。为探明污水厂中PAHs和SPAHs的存在性及不同二级处理和再生水处理工艺对它们的去除效果,对北京及广东共4座污水处理厂中PAHs及SPAHs进行了检测,同时对再生水进行了健康风险评价。结果显示:从进水浓度来看,4座污水处理厂中,低环芳烃浓度(191.8~394.2 ng·L~(-1))明显高于高环芳烃(89.3~108.2 ng·L~(-1));SPAHs中氧取代物(OPAHs)总浓度(253.8~322.2 ng·L~(-1))高于甲基取代物(MPAHs,44.3~220.4 ng·L~(-1))。不同二级处理工艺对PAHs的去除率为43.7%~58.2%,对SPAHs的去除率为45.8%~52.1%。不同再生水处理工艺对PAHs和SPAHs去除率差别较大,PAHs的去除率范围为1.8%~41.1%,SPAHs的去除率范围在2.35%~25.9%。结果表明,目标物的去除以生物降解为主,此外,吸附在固体颗粒上,随颗粒沉淀去除也是主要途径之一。通过对污水厂再生水的风险评价,苯并[a]芘(BaP)和二苯并[a,h]蒽(DBA)2种强致癌物TEQ浓度均高于1,其致癌风险较大,安全性有待提高。     

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.     

Verhalten von PAK im system boden/Pflanze

The results of lysimeter experiments conducted since 1991 dealing with the behavior of PAH in soil/plant systems demonstrate that the PAH pollution to cultivated plants may be caused by both atmospheric deposition and by the soil-to-plant transfer observed in contaminated sites. In the latter, a “direct contamination” of plant surfaces with PAH-loaded soil particles and the subsequent PAH turnover by desorption/adsorption processes is seen to dominate—at least for the most relevant PAHs toxic to humans, benzo(a)pyrene and dibenz(a,h)anthracene. Leafy vegetables growing close to the soil surface are therefore endangered most by a PAH contamination of the soil. The soil-to-plant transfer via “direct contamination” can be reduced to a high degree by covering the contaminated soil with different mulch materials. Systematic PAH transfer via root uptake could not generally be observed. From the reported results, a trigger value in the soil of 1 mg·kg^?1 for benzo(a)pyrene is proposed to make a judgement on PAH contaminated soils with regard to the soil-to-plant transfer pathways. Soils with excessive concentrations of benzo(a)pyrene demand special attention when considering the recommendations for the growth and consumption of cultivated vegetables. The “soil”as well as the “deposition pathways” must be integrated into a complete risk assessment of locations with food plant production, especially in urban areas.