Biodegradation of polycyclic aromatic hydrocarbons (PAHs) by fungal enzymes: A review

Polycyclic aromatic hydrocarbons (PAHs) are a large group of chemicals. They represent an important concern due to their widespread distribution in the environment, their resistance to biodegradation, their potential to bioaccumulate and their harmful effects. Several pilot treatments have been implemented to prevent economic consequences and deterioration of soil and water quality. As a promising option, fungal enzymes are regarded as a powerful choice for degradation of PAHs. Phanerochaete chrysosporium, Pleurotus ostreatus and Bjerkandera adusta are most commonly used for the degradation of such compounds due to their production of ligninolytic enzymes such as lignin peroxidase, manganese peroxidase and laccase. The rate of biodegradation depends on many culture conditions, such as temperature, oxygen, accessibility of nutrients and agitated or shallow culture. Moreover, the addition of biosurfactants can strongly modify the enzyme activity. The removal of PAHs is dependent on the ionization potential. The study of the kinetics is not completely comprehended, and it becomes morem hallenging when fungi are applied for bioremediation. Degradation studies in soil are much more complicated than liquid cultures because of the heterogeneity of soil, thus, many factors should be considered when studying soil bioremediation, such as desorption and bioavailability of PAHs. Different degradation pathways can be suggested. The peroxidases are heme-containing enzymes having common catalytic cycles. One molecule of hydrogen peroxide oxidizes the resting enzyme withdrawing two electrons. Subsequently, the peroxidase is reduced back in two steps of one electron oxidation. Laccases are copper-containing oxidases. They reduce molecular oxygen to water and oxidize phenolic compounds.     

Tissue distribution of perfluoroalkyl acids and health status in wild Mozambique tilapia (Oreochromis mossambicus) from Loskop Dam, Mpumalanga, South Africa

This study examined concentrations of 15 perfluoroalkyl acids (PFAAs) in tissues from male Mozambique tilapia (Oreochromis mossambicus) collected at Loskop Dam, Mpumalanga, South Africa in 2014 and 2016. Nine of the 15 PFAAs were detected frequently and were included in statistical analysis and included two of the most commonly known PFAAs, perfluorooctanesulfonic acid (PFOS) (median, 41.6 ng/g) and perfluorooctanoic acid (PFOA) (median, 0.0825 ng/g). Of the tissues measured, plasma (2016 and 2014 median, 22.2 ng/g) contained the highest PFAA burden followed by (in descending order): liver (median, 11.6 ng/g), kidney (median, 9.04 ng/g), spleen (median, 5.92 ng/g), adipose (median, 2.54 ng/g), and muscle (median, 1.11 ng/g). Loskop Dam tilapia have been affected by an inflammatory disease of the adipose tissue known as pansteatitis, so this study also aimed to investigate relationships between PFAA tissue concentrations and incidence of pansteatitis or fish health status. Results revealed that healthy tilapia exhibited an overall higher (p-value < 0.05) PFAA burden than pansteatitis-affected tilapia across all tissues. Further analysis showed that organs previously noted in the literature to contain the highest PFAA concentrations, such as kidney, liver, and plasma, were the organs driving the difference in PFAA burden between the two tilapia groups. Care must be taken in the interpretations we draw from not only the results of our study, but also other PFAA measurements made on populations (human and wildlife alike) under differing health status.     

多环芳烃在冬小麦体内的吸收与转运及富集研究进展

多年来以煤炭为主的能源消费结构和经济社会持续发展,导致我国PAHs(多环芳烃)排放量居高不下,直接造成土壤和大气PAHs严重污染.为了探明PAHs在冬小麦体内的积累过程和调控机制,在系统分析PAHs在冬小麦体内的吸收、转运和富集的基础上,重点阐述了冬小麦PAHs根系吸收和叶面吸收影响因素方面的最新研究进展.研究发现:① 小麦根系对PAHs的吸收包括主动吸收和被动吸收两种方式,其中主动吸收是一个载体协助、消耗能量、PAHs与H+共运的过程;被动吸收除了在高等植物中普遍存在的简单扩散外,水-甘油通道也参与了该过程. ② PAHs通过气态、颗粒态沉降到小麦叶面角质层或直接通过气孔进入叶片. ③ 影响PAHs根系和叶面吸收的主要因素包括PAHs理化性质、植物生理状况、环境因素等. ④ 小麦根系吸收的PAHs可以向地上部转运,并且与辛醇-水分配系数(K_OW)、蒸腾速率、土壤中氮的形态和浓度有关.主要问题:① 对于小麦叶片吸收的PAHs向基运输机理有待进一步研究. ② 农田生态系统中冬小麦往往遭受土壤及大气双重污染,根系吸收及叶面吸收分别对其体内积累PAHs的贡献尚不清楚.因此,需关注韧皮部、木质部在PAHs转运中所起的作用;利用同位素示踪、双光子激发显微镜等先进技术观察和跟踪PAHs如何进入小麦以及在小麦叶中的转移和分布,阐明PAHs叶面吸收的微观机理;注重大田试验研究,为揭示冬小麦对PAHs的吸收、积累及调控机理,同时也为有机污染地区生产安全农产品提供重要依据.      

南京冬季市区和郊区气溶胶中PAHs浓度的昼夜特征及粒径分布

为了研究南京市区与郊区气溶胶中多环芳烃(PAHs)污染状况和分布特征,利用气-质联用仪(GC-MS)分析了2010年1月1～10日日间和夜间分别在南京大学和南京信息工程大学采集的气溶胶样品,得到南京市区与郊区17种PAHs浓度,总浓度分别为41.36～220.35 ng.m-3和45.10～200.86 ng.m-3,其中约66%～67%分布于细粒子(Dp≤2.1μm)中.研究发现,南京市区和郊区气溶胶中PAH总浓度均处于较高的水平;但两者昼夜变化趋势不同,即市区PAH总浓度日间高于夜间,郊区PAH总浓度日间低于夜间.主导风向的改变和高压天气系统对PAH浓度变化影响较大;在市区其影响主要表现在细粒子部分,而郊区主要表现在粗粒子部分.市区和郊区不同环数的PAHs粒径分布不同;2～3环PAHs,郊区含量高于市区;而4～6环PAHs,市区含量高于郊区.高环数(4～6环)PAHs在粗模态出现较大浓度峰可能是由于南京地区粗模态气溶胶中碳含量较高.市区和郊区相似的特征比值说明两者的PAHs具有相同污染来源,主要为生物质及煤的燃烧和汽车尾气,表明南京市区PAHs受到郊区工业源排放影响较大.     

降解蒽嗜盐菌AD-3的筛选、降解特性及加氧酶基因的研究

蒽是典型的多环芳烃类环境污染物,属于美国EPA优先控制的16种多环芳烃类化合物,其在高盐环境下的生物降解备受关注.本研究从某石油污染的高盐土壤中成功筛选出了1株高效降解蒽的菌株,经过对其生理生化特征和16S rDNA序列分析,初步鉴定并命名该菌株为Martelella sp.AD-3.该菌株在0.1%～10%的盐度和6.0～10.0的pH范围内,均能够降解蒽.其生长和降解蒽的优化条件是:蒽初始浓度25 mg·L-1、温度30℃、pH值9.0和盐度3%,在优化条件下培养6 d,蒽的降解率可达到94.6%.根据已报道的双加氧酶α亚基的同源性设计简并引物,通过巢式PCR扩增获得双加氧酶基因的部分序列307 bp(GenBank:JF823991.1),与海杆菌属Marinobacter sp.NCE312(AF295033)菌株萘双加氧酶大亚基的部分氨基酸序列同源性最高为95%.     

民用燃煤源中多环芳烃排放因子实测及其影响因素研究

民用燃煤是我国目前关注较多的多环芳烃(polycyclic aromatic hydrocarbons,PAHs)排放源.根据我国民用燃煤所涉及的煤种、燃烧方式和炉灶类型,利用全流稀释采样系统对5种不同成熟度的煤种,分别以散块煤和蜂窝煤形式在3种炉灶类型中燃烧产生的烟气进行了采样和分析,初步获取了我国民用燃煤烟气中PAHs排放因子(EFPAHs)的实测数据.结果表明,烟煤的EFPAHs在块煤燃烧方式下的变化范围为1.1～3.9 mg.kg-1,在蜂窝煤燃烧方式下的变化范围为2.5～21.1 mg.kg-1,无烟煤的EFPAHs在块煤与蜂窝煤燃烧方式下分别为0.2 mg.kg-1与0.6 mg.kg-1.在民用燃煤的EFPAHs的各种影响因素中,煤的地质成熟度起主导作用,不同成熟度煤种的EFPAHs差异幅度高达1～2个数量级.其次是燃烧形态(块煤/蜂窝煤),主要表现为同一种地质成熟度的煤在蜂窝煤燃烧方式下排放的PAHs比块煤高2～6倍.炉灶类型的影响最小.     

东海大气气溶胶中二元羧酸的分布特征及来源

大气气溶胶中的二元羧酸因其在全球气候变化中的潜在作用而受到广泛关注.利用2011年5月12日-6月6日在东海采集的气溶胶样品,分析其中水溶性二元羧酸及常量离子浓度,探讨东海气溶胶中二元羧酸的时空分布特征及来源.结果显示东海大气气溶胶中乙二酸、丙二酸和丁二酸的浓度分别为26.0～1475.5 ng·m-3、0.1 ～61.4 ng·m-3和0.1～132.4 ng·m-3,乙二酸在这3种二元羧酸中的贡献最大,为88.3％.东海气溶胶中二元羧酸浓度的昼夜变化不显著.空间分布整体呈现近海高、远海低的趋势.气团的来源和迁移路径以及气象因素影响气溶胶中二元羧酸的分布,气团来自污染较重的陆源时气溶胶中二元羧酸的浓度较高,气团来自清洁的海洋源时,二元羧酸的浓度则较低;阴雾天气时气溶胶中二元羧酸浓度相对较高,降雨发生时二元羧酸的浓度较低.二元羧酸与常量离子的相关性分析表明,自然源和人为源释放的挥发性有机物质在液相中氧化生成二元羧酸是东海大气气溶胶中二元羧酸的主要源,而汽车尾气和生物质燃烧的一次排放、海洋源以及碱性粗颗粒吸收气体二元羧酸不是主要源.液相中乙醛酸氧化形成的乙二酸和长链二元羧酸氧化形成的乙二酸对东海气溶胶中乙二酸的贡献分别为41％和59％.     

海河流域重污染河流表层沉积物氨基酸组成特征

为探明子牙河水系沉积物氮的主要形态,采用柱前衍生反相高效液相色谱-同位素内标法研究了表层沉积物中20种氨基酸的形态及组成特征.结果表明:子牙河水系沉积物中有机氮是氮的主要存在形态,沉积物有机氮(SON)平均浓度为3114 mg·kg^-1,总水解氨基酸氮(THAAs-N)占SON的45.53%;蛋白类氨基酸氮是THAAs-N的主体,占THAAs-N的90.24%,为沉积物潜在释放氮及矿化氮的主体;子牙河水系表层沉积物氨基酸以甘氨酸(Gly)、脯氨酸(Pro)摩尔含量最高,分别占THAAs的14.70%、10.00 %;根据官能团类型分类,蛋白类氨基酸为主要类别,占THAAs的89.50%;蛋白类氨基酸以中性氨基酸为主,平均含量为THAAs的40.69%;亚氨基酸及非蛋白类氨基酸的含量差异性从侧面反映出水系河流污染物来源;采用Glu/γ-Aba及DI指数判断有机质的降解程度,结果显示子牙河水系大部分区域沉积物有机质降解程度较低.     

Investigation of low-molecular weight organic acids and their spatiotemporal variation characteristics in Hongfeng Lake, China

The identities and concentrations of low-molecular-weight organic acids (LMWOAs) were determined by ion chromatography throughout a 20-m water column in Hongfeng Lake, China. The spatiotemporal variations of LMWOAs and their contributions to dissolved organic matter (DOM) in a research period of 24 hr were also investigated. The results demonstrated that five LMWOAs (lactic, acetic, pyruvic, sorbic, oxalic acid) were detected, and their total concentration and proportion in DOC were 6.55 μmol/L and 7.47%. Their average levels were 2.50, 0.65, 2.35, 0.96 and 0.09 μmol/L, respectively. LMWOAs were higher during daytime (10:00-18:00 on Jun 13, 2008) than nighttime (21:00-6:00 the next morning), in particular 4.99 μmol/L high in the epilimnion ( 1 m water depth), reflecting the fact that direct import from terrigenous sources and photochemical production from humic materials were dominant during LMWOAs’ origin and accumulation. The same factors caused LMWOAs to be 0.63 μmol/L in the epilimnion higher than in the hypolimnion. The rapid decrease of total organic acid (TOA) up until 18:00 mainly resulted from bio-uptake and mineralization in the hypolimnion (>1 m water depth). Pyruvic acid increased with time in the epilimnion and decreased in the hypolimnion, largely related to the two contrary processes of continuous degradation and synthesis of macromolecular organic matter during life materials’ cycle mediated by organisms. Simultaneously, plankton behavior and thermal stratification played a pivotal role in LMWOAs’ behavior in the water column, causing decreasing and increasing profiles. The distribution of LMWOAs represents an interesting resource for biogeochemical research of DOM in aquatic ecosystems.     

Allelopathic effects of gallic acid from Aegiceras corniculatum on Cyclotella caspia

High abundance of algae and eutrophication were observed in mangrove wetlands and these were estimated to be associated with root exudates of some specific mangrove plants to a certain extent.Root exudates form allelopathic effects from mangroves.The main secondary metabolites of Aegiceras corniculatum had been detected to be organic phenolic acids.Gallic acid had been isolated and identified from A.corniculatum.The half-maximal inhibitory concentration of gallic acid on alge Cyclotella caspia was tested as 15.46mg/L.The effects on algal cell morphology were mainly shown as elongated cells,with no apparent cell inclusions,such as oil droplets,chloroplast.At a dose of 2mg/L,gallic acid had a stimulative effect on the specific growth rate of algae on day 3.The contents of malondialdehyde,superoxide dismutase,soluble carbohydrates and chlorophyll a in algal cells showed an overall "low promotion and high suppression".Our results could provide preliminary and valuable reference on the complex influences of mangroves on microecology and microbial communities in the rhizosphere system.