土壤和地下水中多环芳烃生物降解研究进展

多环芳烃是一类普遍存在于环境中的难降解的危险性"三致"有机污染物。受污染的土壤和地下水中的多环芳烃,生物降解是其归宿的主要途径。研究表明,对于土壤中低分子量多环芳烃类化合物,微生物一般以唯一碳源方式代谢;而大多数细菌和真菌对四环或四环以上的多环芳烃的降解作用一般以共代谢方式开始。文章重点论述了多环芳烃的来源、降解多环芳烃的微生物、生物降解机理、影响生物降解的因素以及生物修复方法。认为今后的研究方向是高分子量多环芳烃的降解机理与降解途径,基因工程技术在多环芳烃生物降解方面的应用,以及生物表面活性剂产生的机理及其在实际处理中的应用等。     

土壤多环芳烃污染根际修复研究进展

多环芳烃(polycyclicaromatichydrocarbons,PAHs)是环境中普遍存在的具有代表性的一类重要持久性有机污染物,具“三致性”、难降解性,在土壤环境中不断积累,严重危害着土壤的生产和生态功能、农产品质量和人类健康。修复土壤多环芳烃污染已成为研究的焦点。根际修复是利用植物-微生物和根际环境降解有机污染物的复合生物修复技术,是目前最具潜力的土壤生物修复技术之一。对国内外学者近年来在土壤多环芳烃污染根际修复的效果、根际修复机理和根际修复的影响因素方面的研究进展作了较系统的综述,并分别分析了单作体系、混作体系、多进程根际修复系统和接种植物生长促进菌根际修复系统对土壤多环芳烃的修复效果。指出根际环境对PAHs的修复主要有3种机制:根系直接吸收和代谢PAHs;植物根系释放酶和分泌物去除PAHs,增加根际微生物数量,提高其活性,强化微生物群体降解PAHs。并讨论了影响根际修复PAHs的环境因素如植物、土壤类型、PAHs理化性质、菌根真菌以及表面活性剂等。植物-表面活性剂结合的根际修复技术、PAHs胁迫下根际的动态调节过程、运用分子生物学技术并结合植物根分泌物的特异性筛选高效修复植物以及植物富集的PAHs代谢产物进行跟踪与风险评价将成为未来研究的主流。     

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.     

汕头经济特区土壤中优控多环芳烃的分布

运用气相色谱-质谱方法对汕头经济特区131个土样中的美国EPA优控多环芳烃(PAHs)进行定性、定量测定,讨论了PAHs的分布特征。结果表明,该区表层土壤中优控PAHs的总质量分数范围从22.1 ng/g到1256.9 ng/g之间,平均质量分数为(317.3210.2) ng/g。其分布随采样点的位置不同而有显著变化:工业区附近多环芳烃的质量分数最高,城市中心次之,郊区最低。大多数样点中?PAHs质量分数和单种PAH质量分数都呈现w(5~20 cm)> w(0~5 cm)>w(20~40 cm)>w(40~100 cm)的垂直分布规律。该区土壤PAHs以3环和4环化合物为主,单种PAH以萘、菲和苯并[b]萤蒽为主。     

北京市郊农业土壤中多环芳烃的污染分布和来源

采集了3个北京市郊发展新区(昌平区、大兴区、房山区)共计20个不同类型表层农业土壤样品,通过微波萃取和高效液相色谱分析其中多环芳烃(PAHs)含量.结果显示,研究区表层土壤已受到不同程度的污染,16种优先控制的多环芳烃总含量为1.20—3.35μg.g-1,表层土壤中的多环芳烃主要源于燃烧源,且受燃汽油型汽车尾气的影响更显著.     

红树林生态系统多环芳烃的污染研究进展

多环芳烃（PAHs）是一类广泛存在于天然环境中的持久性有机污染物,对生态环境和人类健康造成严重的潜在威胁。文章介绍了红树林生态系统PAHs污染的研究现状;总结了红树林生态系统PAHs的污染分布及其来源,以及PAHs污染胁迫对红树植物生长的影响;评述了红树植物对PAHs的直接吸收、红树林湿地微生物对PAHs的降解等研究;最后,对红树林生态系统PAHs污染的研究趋势进行了分析和展望,提出了今后可能的研究方向,主要包括：（1）综合应用多学科交叉研究典型PAHs在红树林生态系统中的环境行为;（2）结合双光子激光共焦扫描显微技术等原位研究手段,开展红树植物对典型PAHs的吸收、存赋形态、转运等相关研究;（3）结合激光诱导时间分辨荧光光谱测定系统,实现对现场红树林生态系统中PAHs等有机污染物的原位检测。     

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。     

Concentrations of polycyclic aromatic hydrocarbons in soils of a mangrove forest affected by forest fire

Surface soils affected by forest fires from Igbanko mangrove forest in Nigeria were analyzed for 16 EPA priority polycyclic aromatic hydrocarbons (PAHs) using gas chromatography–mass spectrometry (GC–MS). The total PAHs concentrations in the soils ranged from 63 to 188?µg?kg^?1 dry weight (average: 108?µg?kg^?1). The three predominant PAHs in the soils were naphthalene (Na), fluoranthene (Flu), and benzo(b)fluoranthene (BbF). Compared to the control sample (19?µg?kg^?1), elevated PAHs concentrations were observed in the soils, an indication of some level of PAHs contamination. PAHs source diagnostic ratios of Flu/(Flu?+?Pyr) and Ant/(Ant?+?Phe) indicated that the PAHs have a pyrogenic origin which may have resulted from combustion of grass, wood, or coal. An assessment based on Canadian soil quality guidelines indicated that the studied locations do not pose any serious adverse risk on human health.     

Aryl hydrocarbon receptor activities of hydroxylated polycyclic aromatic hydrocarbons in recombinant yeast cells

Hydroxylated polycyclic aromatic hydrocarbons (OH-PAH) with less than four rings are frequently found in the environment, whereas the toxicities associated with these compounds remain unclear. In this study, aryl hydrocarbon receptor (AhR)–ligand binding activities of OH-PAH were investigated by using a recombinant yeast assay system. The majority of the OH-PAH tested showed AhR–ligand binding activities, especially, when the hydroxylated derivatives of naphthalene were incubated with recombinant yeast. The structure–activity relationship between AhR activity and molecular weight or the octanol–water partition coefficient value of OH-PAH displayed significant correlations. These findings indicate that the site and number of hydroxy-groups substituted on PAH skeleton apparently influenced the AhR – ligand binding activity in the recombinant yeast assay.     

Isolation and identification of fungi tolerant to polycyclic aromatic hydrocarbons and coal tar from different habitats in Lithuania

A group of 36 fungal strains, belonging to the Lithuanian mycobiota, was collected and isolated from different locations, habitats, and matrices, including creosote-treated wood in storage yards for crosstie wastes. The eight most perspective strains selected according to preliminary assessment of tolerance to coal tar were subsequently identified combining taxonomical evaluation and molecular techniques. The tolerance of the eight identified fungal species (five basidiomycetes and three ascomycetes) to the presence of various concentrations of coal tar, and for the four most perspective fungal strains (Pleurotus sp., Schizophyllum sp., Irpex lacteus, Bjerkandera adusta) to polycyclic aromatic hydrocarbons was evaluated. The ligninolytic enzymatic activity assay of the isolated strains resulted in a good correspondence between the tolerance to pollutants and the capability to produce ligninolytic enzymes indicating that this group of white-rot fungi is perspective for further investigation and eventual usage for mycoremediation of polycyclic aromatic hydrocarbons polluted substrates.     

湖北省金罗家考古遗址土壤中多环芳烃的分布和植硅体的分析及其意义

湖北金罗家遗址剖面总厚度为171 cm,平均10 cm采集一个样品,共采集17个样品。考古遗址年代顺序主要根据考古器物（如陶片、瓷片、砖瓦块等）颜色、图案、花纹和形态类型等与已确定年代的考古器物特征进行对比分析,进而确定不同文化层的时代顺序。文章对考古土壤中多环芳烃的分布、植硅体类型和炭屑进行了研究,并对多环芳烃可能来源、植硅体组合和炭屑及其意义进行了分析。结果显示,在最下部的生土层样品未检测到多环芳烃,古文化层土壤样品均检测出了多环芳烃,不同文化层土壤中的多环芳烃的分布特征也是不同的,在个别文化层土壤中的多环芳烃还表现出一些异常。利用多环芳烃来源地球化学参数甲基菲/菲（MPh/Ph）和荧蒽/芘（Fl/Py）的比值对金罗家遗址考古遗址土壤中的多环芳烃的来源进行了初步判断,考古土壤多环芳烃的MPh/Ph值范围主要在0.34~0.89之间（除F13样品值为1.30外）,Fl/Py值范围主要在1.92~5.88之间（除F8样品值为10.82外）,说明多环芳烃的来源主要是热成因。而荧蒽/菲、苯并蒽/菲和苯并芘/菲等可以作为与陆生植物和化石燃料的燃烧有关芳烃的产物的标志,这些多环芳烃可能与人类活动有一定的关系,说明考古遗址土壤中的多环芳烃记录能够反映生活在该遗址上一些人类社会经济发展和活动的信息。因此,多环芳烃是人类活动的良好指示物。同时,在整个剖面土壤中还检测出大量的且种类多样的植硅体和炭屑,植硅体类型主要有：方型、长方型、扇型、哑铃型、鞍型、齿型、帽型、棒型和尖型等。植硅体组合能够恢复当地的古植被,也可以反映古人类在选择和利用植物有关的生活和生产活动。其古植被生长是与古气候变化相适应的,在西周时期文化层,以C3植物为主;东周时期文化层,以C4植物为主;唐宋时期文化层,以C3植物为主,明清时期文化层,以C4植物为主。炭屑是植物有机体不完全燃烧的产物,炭屑分析是研究历史上人类活动的方法之一。在金罗家遗址样品炭屑分析中,从不同古文化堆积层的变化背景中分离出了因人口增长或火灾造成的2个炭屑高峰值,第一个峰值为东周时期,另一峰值为明清时期,这两个峰值与自西周（1 000 BC）以来历史记载的该地区2个人口繁盛和经济发达时间基本相符。在对考古土壤中的多环芳烃、木本型植硅体和炭屑对比分析中,它们的变化规律存在着较好的一致性。这些说明生活在遗址的人类利用和改造自然环境的时候,自然环境也可能影响着人类社会的发展。     

焦化厂污染场地表层土壤有机-矿质复合体中多环芳烃的分布

采用湿法物理分级方法将湖南省某焦化厂遗留场地表层土壤分成4种粒级的有机-矿质复合体组分,即粘粒(<2μm)、粉粒(2—20μm)、细砂(20—200μm)和粗砂(>200μm),并研究了美国EPA优先控制的16种多环芳烃(PAHs)在其中的分布特征及土壤不同有机-矿质复合体组分中有机质和矿物质组成的差异对PAHs赋存分布的影响.研究结果表明,不同粒级有机-矿质复合体中PAHs的含量顺序为粗砂>粉粒>细砂>粘粒,低环PAHs(环数≤3)在粘粒中的含量较高,达到56.3%,而高环PAHs(环数≥4)在粉粒、细砂和粗砂中的分布较高含量分别是79.37%、72.7%和71.63%,各粒级矿质复合体中PAHs含量与土壤有机碳有较好的相关性.通过对有机-矿质复合体进行X射线衍射分析发现,场地土壤粘粒和粉粒中粘土矿物含量较高,这也在一定程度上影响了污染物质在其中的分布.     

Toxic equivalency factor approach for risk assessment of polycyclic aromatic hydrocarbons

The toxic equivalency factor (TEF) method has been developed to evaluate structurally related compounds, sharing a common mechanism of action. Because certain polycyclic aromatic hydrocarbons (PAHs) appear to fit this requirement and are ubiquitous environmental contaminants, these compounds are TEF candidates. Toxicity is often expressed relative to benzo[a]pyrene (BaP), the reference standard (e.g., TEF = EC50_BaP/EC50_PAH). BaP‐like toxicity or toxic equivalents (TEQs) can then be calculated: TEQ = S(PAH _i × TEF _i ), where PAH _i and TEF _i are the concentration and TEF, respectively, for individual PAH congeners. Representative TEFs for PAHs were compiled from studies measuring carcinogenic potency and surrogate biomarkers. This review examines the application of TEFs to PAHs with established criteria (i.e., demonstrated need, defined chemical grouping, broad toxicological database, endpoint consistency, additivity, common mechanism of action, consensus). Although all criteria are not satisfied (e.g., endpoint inconsistency, nonadditivity) and more rigorous validation studies are needed, the TEF method is useful when limitations are recognized. Refinements of the method might include incorporation of pharmacokinetic factors and segregation of TEFs derived from mammalian vs. nonmammalian systems to increase endopoint consistency. Probabilistic analysis may also prove useful to assess the range of TEF values reported both within and between human health and ecological risk assessments.     

土壤与沉积物对多环芳烃类有机物的吸附作用

吸附作用是疏水性有机物在土壤和沉积物环境中的重要迁移转化行为之一。多环芳烃是环境中一种重要的疏水性有机污染物。文章着重阐述了多环芳烃类有机物在土壤和沉积物中有机质和粘土矿物吸附机理，指出土壤、沉积物有机质的结构异质性是导致非线形吸附的重要原因；分析了影响多环芳烃吸附过程的诸多因素，并提出该研究领域存在的问题以及今后发展的方向。     

Accumulation and phytoavailability of benzo[a]pyrene in an acid sandy soil

Effects of benzo[a]pyrene (B[a]P) on ryegrass (Lolium perenne L.) growth, plant accumulation and dissipiation of B[a]P in a red sandy soil (Hapli-Udic Argosol) were studied in a pot experiment. The plants were grown for 61 days in soil spiked with B[a]P at 0, 12.5, 25 and 50 mg kg⁻¹. Control pots without plants were also set up. Soil extractable B[a]P, plant shoot and root biomass, and concentrations of B[a]P in plant shoots and roots were determined. Ryegrass biomass was increased by addition of B[a]P and root B[a]P concentrations were significantly correlated with B[a]P application rate, but no such correlation was found for shoot B[a]P concentrations. This indicates that B[a]P enhanced the growth of the ryegrass. The extractable B[a]P concentration in the planted soil was significantly lower than that in the unplanted control soil at the rate of 50 mg B[a]P kg⁻¹. This indicates that ryegrass may help to dissipate B[a]P in soil at concentrations over 50 mg kg⁻¹ soil although the mechanism for this is not understood.     

Application of probabilistic risk assessment at a coking plant site contaminated by polycyclic aromatic hydrocarbons

Application of Probabilistic Risk Assessment （PRA） and Deterministic Risk Assessment （DRA） at a coking plant site was compared. By DRA, Hazard Quotient （HQ） following exposure to Naphthalene （Nap） and Incremental Life Cancer Risk （ILCR） following exposure to Benzo（a）pyrene （Bap） were 1.87 and 2.12 × 104. PRA revealed valuable information regarding the possible distribution of risk, and risk estimates of DRA located at the 99.59th and 99.76th percentiles in the risk outputs of PRA, which indicated that DRA overestimated the risk. Cleanup levels corresponding acceptable HQ level of 1 and ILCR level of 104 were also calculated for both DRA and PRA. Nap and Bap cleanup levels were 192.85 and 0.14mg.kg-1 by DRA, which would result in only 0.25% and 0.06% of the exposed population to have a risk higher than the acceptable risk, according to the outputs of PRA. The application of PRA on cleanup levels derivation would lift the cleanup levels 1.9 times for Nap and 2.4 times for Bap than which derived by DRA. For this coking plant site, the remediation scale and cost will be reduced in a large portion once the method of PRA is used. Sensitivity analysis was done by calculating the contribution to variance for each exposure parameter and it was found that contaminant concentration in the soil （Cs）, exposure duration （ED）, total hours spent outdoor per day （ETout）, soil ingestion rate （IRs）, the air breathing rate （IRa） and bodyweight （BW） were the most important parameters for risk and cleanup levels calculations.     

新乡市地表水中多环芳烃的分布特征及生态风险

利用GC-MS测定了新乡市地表水中15种多环芳烃(PAHs)的含量,分析了其组成特征,并通过安全阈值(MOS10)法评价了新乡市地表水中PAHs的生态风险.结果表明,新乡市地表水中PAHs的含量为369—4248 ng·L,与国内其他河流相比,污染水平较高.PAHs的组成以3环和4环为主,分别占总量的41.3%和40.3%.新乡市地表水中单种PAHs对水生生物的生态风险大小依次为蒽(Ant)菲(Phe)芘(Pyr)苯并[a]芘(Ba P)荧蒽(Flua)芴(Flu)苊(Ace),其中Ant和Phe的暴露浓度超过影响10%水生生物的概率分别为30.2%和10.4%,具有潜在生态风险;Ace、Flu、Flua、Pyr和Ba P的暴露浓度超过影响10%的水生生物的概率分别为0.85%、1.96%、4.26%、6.71%和5.69%,生态风险较低.联合生态风险评价结果表明,新乡市地表水中∑PAH7等效浓度超过影响10%水生生物的概率为43.7%,大于任何单种PAHs对水生生物的生态风险,主要河流的生态风险从大到小依次为金堤河(56.6%)共产主义渠(43.0%)天然文岩渠(16.4%).     

Concentration of some polycyclic aromatic hydrocarbons in rain,soil and ground water around Ismailia,Egypt

Residues of acenaphthylene, fluorene, anthracene, pyrene, chrysene, benzo(b)fluoranthene and benzo(k)fluoranthene were monitored in rain, soil and groundwater around Ismailia, in northeast Egypt. Residues detected in rain water in 1995 and 1996 were mainly of relatively low molecular weight. Both acenaphthylene and fluorene were detected in rain for the two consecutive years. Top soil has shown a wider spectrum and higher concentrations of (PAHs) than those detected in deep soil, rain and ground water. Only three compounds, acenaphthylene, fluorene and anthracene were detected in samples collected at 50 cm depth. While no traces of PAHs were detected at 1 m depth detectable concentrations of fluorene and anthracene were monitored in groundwater.     

安普霉素对不同土壤中微生物活动的影响

研究了兽药抗生素安普霉素对不同土壤中微生物呼吸活动和对土壤中微生物种群生长的影响，了解该药物对土壤生态系统生态毒理学效应，以便为药物的环境安全性评价提供依据。利用直接吸收法(密闭法)测定安普霉素对土壤微生物呼吸活动的影响，结果表明：安普霉素对不同土壤中微生物呼吸活动的影响有所差异。在污染的中后期，长春土中加入一定量的安普霉素能刺激土壤的呼吸作用。在染毒的前期，安普霉素对成都土中CO2的释放量均有抑制作用。采用稀释平板法测定了药物对不同土壤中细菌、真菌生长的影响。实验结果显示：安普霉素对土壤中的细菌的生长具有明显的抑制作用，成都土和长春土的抑菌作用最为明显；同时安普霉素的这种抑制作用还表现出时间差异，24h的抑制率高于48h。安普霉素对土壤中真菌生长的影响表现出地域差异，低质量分数的安普霉素对成都土和武汉土中的真菌没有抑制作用。在所测的四种土壤中，南京土中药物对真菌的平均抑制率最高。这可能与土壤中微生物的种类和种群结构有关。安普霉素对不同土壤中对真菌的抑制作用，随药物质量分数的降低和作用时间的延长而降低。     

Distribution of Airborne polycyclic aromatic hydrocarbons (PAH) in the area of Thessaloniki,Greece

The aim of this research work is to investigate the temporal and regional behaviour of the PAH in the Thessaloniki's area. During a period of six months, airborne particulate matter was collected twice a week and PAH were determined by HPLC. Profiles as well as concentrations of selected cancerogenic PAH differ in some cases from area to area and have characteristic, temporal changes of concentration.