镉—多环芳烃复合污染土壤植物修复的强化作用及机理
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摘要
随着我国工业化和城市化进程的发展,环境中重金属和有机污染物的排放量在相当长的时间内会保持在比较高的水平,我国土壤污染也将因此趋向严重化和复杂化。根据近年来的一些报道,我国许多区域的土壤中存在重金属-有机物复合污染。针对我国土壤污染治理出现的新的问题和挑战,发展环境友好、成本低廉且的原位修复技术是亟待解决的问题。本研究以我国土壤典型污染物镉(cadmium, Cd)和多环芳烃(polycyclic aromatic hydrocarbons, PAHs)为代表,研究了Cd和PAHs在复合污染过程中的相互作用及其对我国原生Cd超积累植物东南景天(Sedum alfredii)对复合污染修复效应的影响,并通过农艺、化学和微生物等措施开展了Cd-PAHs复合污染土壤植物修复强化技术及机理的研究,取得的主要研究结果如下:
     (一)采用室内培养试验模拟Cd和PAHs在土壤复合污染过程中的对彼此环境行为的影响。研究结果表明,土壤中苯并[α]芘(benzo[a]pyrene, B[a]P)的消散主要是通过微生物降解途径。高Cd浓度(25mgkg-1)对土壤中B[α]P的降解有明显的抑制作用,加入初始浓度为250mg kg-1的芘(pyrene, PYR)能显著促进B[α]P的降解,缩短其半衰期并缓减高Cd浓度对B[α]P的降解的抑制。解吸态和非解吸态B[α]P对其在土壤中的降解均有贡献且可以相互转化,其中解吸态B[α]P的贡献率较大,而残留态B[α]P对总降解量的贡献可以忽略。因PYR的加入而促进降解的那部分B[α]P主要为解吸态。加入PYR在250天的培养过程中未对土壤中水提取态和有效态(醋酸铵提取态)Cd浓度产生显著影响,高Cd浓度土壤中水提取态和有效态Cd浓度受到老化作用的影响,在培养后期有下降趋势。
     (二)采用盆栽试验研究了我国原生Cd超积累植物东南景天在Cd-PHE (phenanthrene,菲)/PYR复合污染土壤中的生长及其对两类污染物的去除能力。供试土壤为轻度Cd污染的菜地土壤(0.92mg kg-1),分别指设置2个Cd污染浓度(0.92,6mgkg-1)和3个PHE/PYR污染浓度(0,25,150mgkg-1),并将各个Cd和两种PAHs的污染水平分别进行交叉处理。在各个复合污染浓度土壤中种植东南景天并设置无植物对照。研究结果表明,土壤Cd浓度的提高促进了东南景天的生长,但是PAHs的存在抑制了这种促进作用。同时,在高浓度Cd污染土壤中PAHs还抑制了东南景天对Cd的吸收积累并降低了Cd的植物提取效率。经过60天的种植,土壤Cd的植物去除率在低、高浓度Cd污染土壤中分别为5.8~6.7%和5.7~9.6%。PHE和PYR的去除率在种植东南景天后的土壤和无植物对照土壤中并无显著差异。土壤Cd浓度的提高抑制了PYR在土壤中的降解消散,同时也抑制了脱氢酶活性,这说明Cd对PYR降解的抑制可能是由其对土壤微生物活性的抑制作用引起的。本试验的结果说明东南景天可以在PHE或PYR存在下,从土壤中有效提取Cd,但是在高浓度Cd污染土壤中,其提取效率受到两种PAH的抑制。另一方面,仅种植东南景天不足以同时修复土壤中的PAH,其他强化措施需要被引入以达到共同去除Cd和PAH的目的。
     (三)通过盆栽试验,研究了有机肥(猪粪蚯蚓堆肥产物,pig manure vermicompost)强化东南景天修复Cd-PAHs复合污染土壤的潜力。在Cd浓度为5.53mg kg-1的土壤中添加三种代表性的PAHs (PHE、PYR和蒽(anthracene, ANT),每种目标浓度均为250mgkg-1)。试验设置四个处理:1)无植物且不施用有机肥的土壤;2)种植东南景天但不施用有机肥的土壤;3)施用有机肥但不种植东南景天的土壤;4)施用有机肥且种植东南景天的土壤。研究结果表明,施用有机肥使东南景天地上部和根部的干物质重分别是未施肥处理的2.17和3.93倍,但没有对植物地上部Cd浓度产生显著影响。施肥处理中Cd的植物提取效率是未施肥处理的1.97倍。施用有机肥不但对土壤酶活没有抑制作用,反而增高了土壤微生物生物量碳。与无植物无肥料对照相比,施用有机肥且种植东南景天分别将PHE、PYR和ANT的去除率提高了0.26%、3.21%和4.00%,但是单独施用有机肥或种植东南景天对PAHs的消散没有促进作用。土壤中的PAH降解菌的相对丰度与PAHs的去除率没有显著相关性。施用有机肥且种植东南景天显著改变了土壤总细菌群落结构和多样性,相对较高的PAHs去除率可能是由于有机肥与植物根系相互作用改变了根际土壤的微生物群落结构使其更有利于PAHs降解。综上所述,种植东南景天并施用有机肥能有效去除Cd-PAHs复合污染土壤中的两类污染物。
     (四)通过盆栽试验比较了东南景天-黑麦草(Lolium perenne)、东南景天-蓖麻(Ricinus communis)套作体系与东南景天单作体系对Cd-PAH复合污染土壤中Cd、锌(Zn)和铅(Pb)的提取效率和PHE、PYR和ANT的去除率。研究结果表明,与蓖麻套作降低了东南景天地上部的生物量。与黑麦草和蓖麻套作分别使东南景天地上部的Cd浓度比单作处理中下降了64.3%和47.4%,相反,与黑麦草和蓖麻套作分别使东南景天地上部的Zn浓度比单作处理中提高了19.8%和25.6%。与黑麦草套作的东南景天地上部Pb浓度显著高于单作处理。总体上,三种植物系统对Cd、Zn和Pb的总提取量没有显著差异(除了东南景天-黑麦草套作系统对Pb的提取量最高)。两种套作体系中土壤PYR和ANT的去除率显著高于东南景天单作体系和无植物对照。与无植物对照相比,东南景天-黑麦草和东南景天-蓖麻套作系统分别把土壤中PYR的去除率提高了2.3%和3.5%,而ANT的去除率则分别提高了8.5%和9.1%。这可能是因为套作体系促进了土壤微生物的生长和主要氧化还原酶活性。综上所述,东南景天-黑麦草、东南景天-蓖麻套作体系是从复合污染土壤中同时去除重金属和PAHs的有效措施。
     (五)通过盆栽试验研究了非离子表面活性剂Tween80、B[a]P降解菌剂及两者联合施用对东南景天修复Cd-B[a]P复合污染土壤的影响。研究结果表明,Tween80、B[a]P降解菌剂和两者联合作用均未对植物生长和Cd提取效率产生显著影响。东南景天对低、高两个Cd水平的Cd-B[a]P复合污染土壤中Cd的提取效率分别为16.8-20.8%和6.4-7.6%。总体上,施用菌剂能促进土壤中B[α]P的降解,而Tween80对B[α]P去除率的影响受到土壤Cd浓度水平和植物相互作用的影响。在高Cd浓度(4.71mg kg-1)土壤中,菌剂-表面活性剂协同作用能最有效地去除B[α]P。东南景天-菌剂联合修复能同时并有效地去除土壤中的Cd和B[α]P,而Tween80-菌剂-东南景天联合作用在高Cd浓度水平的Cd-B[a]P复合污染土壤中能最高效地同时去除两种污染物。
Soil contamination by heavy metals and persistent organic pollutants has been accelerated in China during the past decade because of rapid urbanization and industrialization. The output of heavy metals and organic pollutants into environment will stay in a comparatively high level in a long period. Soil contamination in China tends to be severe and complicated. Cadmium (Cd) and polycyclic aromatic hydrocarbons (PAHs) are of particular concern due to their persistence; potentially carcinogenic, mutagenic, and teratogenic properties; and their ubiquitous occurrence in the environment. Sites co-contaminated by heavy metals and PAHs, in many regions, e.g. Shen-Fu Irrigation Area located between Shenyang and Fushun City in Liaoning Province of China, have been documented in recent. Therefore, the need to develop environmental friendly, low-cost, and in situ strategies directed at co-contaminated sites is of great importance. This study investigated the interaction between Cd and PAHs during the process of soil co-contamination and their effects on phytoremediation of Cd-PAHs co-contaminated soil by a Cd hyperaccumulator Sedum alfredii native to China. Agronomic, chemical, and microbial strategies were also investigated to improve phytoremediation of Cd-PAHs co-contaminated soils. The main results are summarized in the following text:
     (1) A microcosmos incubation experiment was conducted to investigate the interaction between Cd and PAHs during the process of soil co-contamination. The dissipation of benzo[a]pyrene (B[a]P) in soil was mainly due to microbial degradation. High Cd concentration (25mg kg-1) significantly inhibited the degradation of B[a]P in the soil, and the addition of pyrene (PYR) with an initial concentration of250mg kg-1remarkably promoted B[a]P degradation. Both desorbing and non-desorbing fractions of B[a]P contributed to B[a]P degradation in soil; however, desorbing fraction contributed more as compared to non-desorbing fraction. The contribution of residual fraction to B[a]P degradation could be negligible. Desorbing fraction of B[a]P could transform into non-desorbing fraction and vice versa. The loss of B[a]P promoted by Addition of PYR was mainly attributed to desorbing fraction. During250days' incubation, the addition of PYR did not affect the concentrations of water-extractable and available Cd (N H4OAc-extractable) in soils, whereas aging effects decreased the concentrations of both Cd fractions in high Cd treatments in the later incubation period.
     (2) A Pot experiment was conducted to investigate the growth of S. alfredii and removal of contaminants from Cd-PAHs co-contaminated soil. Soil slightly contaminated by Cd (0.92mg kg-1) was collected from a vegetable field in Hangzhou and was spiked with two levels (0and6mg kg-1) of Cd and three levels (0,25and150mg kg-1) of phenanthrene (PHE) or PYR. Elevated Cd level (6.38mg kg-1) increased S. alfredii growth. The presence of PAHs decreased the stimulatory effects of Cd on plant biomass and Cd concentrations in shoots in Cd spiked soil, thus decreasing Cd phytoextraction efficiency. Cadmium removal by S. alfredii after60d of growth varied from5.8to6.7%and from5.7to9.6%, in Cd unspiked and spiked soils, respectively. Removal rate of PAHs in the soil was similar with or without the plants. Pyrene removal rate in the soil with elevated Cd. This appears to be due to decrease in soil microbial activity, which is confirmed by the decrease in DHA, which is a good indicator of soil microbial activity. The results demonstrate that S. alfredii could effectively extract Cd from Cd-contaminated soils in the presence of PHE or PYR; however both PAHs exhibited negative effects on phytoextraction of Cd from Cd spiked soil (6.38mg kg-1). Sedum alfredii is not suitable for remediation of PAHs. Additional strategies are needed to accomplish simultaneous removal of Cd and PAHs from co-contaminated soils by S. alfredii. The effects of Cd and PAHs concentrations on the removal rate of PAHs appear to be attributed to the changes in microbial activities in the soil.
     (3) A pot experiment was conducted to investigate the potential for enhanced phytoextraction of Cd by S. alfredii and dissipation of PAHs in co-contaminated soil by application of pig manure vermicompost (PMVC). Soil contaminated by Cd (5.53mg kg-1) was spiked with PHE, anthracene (ANT) and PYR together (250mg kg-1for each PAH). The pot experiment was conducted in a greenhouse with four treatments:1) soil without plants and PMVC (Control),2) soil planted with S. alfredii (Plant),3) soil amended with PMVC at5%(w/w)(PMVC), and4) treatment2+3(Plant+PMVC). Application of PMVC to co-contaminated soil increased the shoot and root dry biomass of S. alfredii by2.27-and3.93-fold, respectively, and simultaneously increased Cd phytoextraction efficiency by1.97-fold without inhibiting soil microbial population and enzyme activities. The highest dissipation rate of PAHs was observed in Plant+PMVC treatment. The dissipation rates of PHE, PYR and ANT were significantly higher by0.26,3.21and4.00%, respectively, as compared to the control. However, neither S. alfredii nor PMVC enhanced PAHs dissipation when applied separately. Abundance of PAH-degraders in soil was not significantly related to PAHs dissipation rate. Plant+PMVC treatment significantly influenced the bacterial community structure. Enhanced PAHs dissipation in the Plant+PMVC treatment could be due to the improvement of plant root growth, which may result in increased root exudates, and subsequently change bacterial community structure to be favorable for PAHs dissipation. This study demonstrated that remediation of Cd-PAHs co-contaminated soil by S. alfredii can be enhanced by simultaneous application of PMVC.
     (4) A pot experiment was conducted to investigate the potential for phytoextraction of heavy metals and rhizoremediaiton of PAHs in co-contaminated soil by co-planting S. alfredii with ryegrass(Lolium perenne) or castor (Ricinus communis). Co-planting with castor decreased the shoot biomass of S. alfredii as compared to that in monoculture. Cadmium concentration in the S. alfredii shoot decreased by64.3and47.4%, respectively, in S-R and S-C treatments, as compared to that in S. alfredii monoculture. In contrast, Zn concentration in the S. alfredii shoot increased by19.8and25.6%, respectively, in S-R and S-C treatments, as compared to that in S. alfredii monoculture. Lead concentration in S. alfredii shoot in S-R treatment was significantly greater as compared to that in S. alfredii monoculture. Total removal of either Cd, Zn or Pb by plants was similar across S. alfredii monoculture or co-planting with ryegrass or castor, except for the enhanced Pb removal in S. alfredii and ryegrass co-planting treatment. Co-planting of S. alfredii with ryegrass or castor significantly enhanced the PYR and ANT dissipation as compared to that in the control soil or S. alfredii monoculture. The dissipation rate of PYR was greater by2.3and3.5%, respectively, in S-R and S-C treatments as compared to that in the control soil. The dissipation rate of ANT was greater by8.5and9.1%, respectively, in S-R and S-C treatments as compared to that in the control soil. This appears to be due to the increased soil microbial population and enzyme activities in both co-planting treatments. Co-planting of S. alfredii with ryegrass or castor provides a promising strategy to mitigate both metal and PAH contaminants from co-contaminated soils.
     (5) A pot experiment was conducted to investigate the single and combined effects of non-ionic surfactant (Tween80) and B[a]P-degrading bacteriums on phytoremediation of soils co-contaminated with Cd and high-molecular-weight PAH (B[a]P) by S. alfredii. Neither separate nor combined application of Tween80and B[a]P-degrading bacteriums significantly affected plant growth and Cd uptake and accumulation by plant. However, S. alfredii can effectively extract Cd from co-contaminated soil. Cadmium phytoextraction rate after120d of growth varied from16.8to20.8%and from6.4to7.6%, respectively, in Cd unspiked and spiked soils. In genaral, the application of B[a]P-degrading bacteriums can enhance B[a]P dissipation in soil. However, the effects of Tween80on B[a]P dissipation were influenced by the interaction between soil Cd concentration and plant. In the soil with high Cd concentration (4.71mg kg-1), the combined application of of Tween80and B[a]P-degrading bacteriums could remove B[a]P most effectively in both planted and unplanted treatments. These results demonstrated that decontaminaton of Cd and B[a]P can be achieved by S. alfredii associated with B[a]P-degrading bacteriums; however, the combined application of Tween80and B[a]P-degrading bacteriums can remove B[a]P more efficiently from soil with relatively higher Cd concetration (4.71mg kg-1). The complicated interactions among Tween80, B[a]P-degrading bacteriums and soil Cd concentration on the competition between B[a]P-degrading bacteriums and indigenous microbial community need future investigations.
引文
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