Biodegradation and kinetic analysis of phthalates by an Arthrobacter strain isolated from constructed wetland soil

A bacterial strain C21 isolated from constructed wetland soil was identified as Arthrobacter sp. based on 16S rRNA gene sequence analysis and physio-biochemical characteristics and was capable of utilizing di-n-butyl phthalate (DBP) as a carbon and energy source for growth. Strain C21 can also utilize other phthalates (PAEs) up to a molecular weight of 390.56 and phthalic acid (PA). The biodegradability of these compounds decreased with the increase in the length of phthalate alkyl chains and molecular weight. Kinetic analysis indicated that the strain C21 cell growth on DBP fitted well with Haldane-Andrews’ model (R ²?>?0.98) with μ _max, K _s, and K _i of 0.12/h, 4.2 mg/L, and 204.6 mg/L, respectively. When the initial DBP concentration was lower than 100 mg/L, DBP biodegradation reaction fitted with the first-order kinetics. The results suggested that Arthrobacter strain C21 played an active role in the bioremediation of the wetland contaminated with phthalates.     

A comparison of bacterial removal efficiencies in constructed wetlands and algae-based systems

Constructed wetlands and algae-based systems have been compared regarding their efficiencies on faecal bacteria removal. Two types of constructed wetlands, sub-surface (SSF) and free water surface (FWS) flow systems, and two more types of algae-based systems, high rate algae ponds (HRAP) and maturation pond (MP) have been studied for two years. All systems treated the same wastewater from a rural locality in León (northwest of Spain). Hydraulic retention time was 3 days for both wetland systems, 20 days for the maturation pond and 10 days for the high rate algae pond. Total coliforms, faecal coliforms, faecal Streptococci, Clostridium perfringens, and Staphylococci were analyzed in the influent and effluents of each system. A comparison among the wetland systems showed that SSF were more efficient than FWS system when considering surface removal rates (cfu removed/m²/d). Nevertheless, differences were not statistically significant. Considering mean removal efficiencies (in log unit), results showed that higher reductions were observed in FWS for most of the groups except for clostridia and Staphylococci. Concerning algae-based systems, MP showed higher removal efficiencies than HRAP, getting higher surface removal rates in the HRAP. Generally constructed wetlands were more efficient than algae-based systems when considering both, efficiencies in % and surface removal rates.     

Comparison on the removal of phthalic acid diesters in a bioreactor landfill and a conventional landfill

The removal of phthalic acid diesters (PAEs) in municipal solid waste (MSW) from two simulated landfill reactors was compared. The results showed that the original concentrations of dimethyl phthalate (DMP), dibutyl phthalate (DBP) and dioctyl phthalate (DOP) in the refuse were 3.3 μg g⁻¹, 18.5 μg g⁻¹ and 0.8 μg g⁻¹, respectively. The concentrations of DMP and DBP in both leachate and refuse decreased greatly during decomposition of the waste in both reactors. The major loss of PAEs from the landfill occurred during an active methanogenic environment with a low concentration of volatile fatty acids (VFA) in the later period. In addition, strong correlations were found between the residual DMP, DBP concentrations and the biologically degradable material (BDM) of the refuse. Finally, PAEs degraded more rapidly in the landfill that was operated in conjunction with the methanogenic reactor when compared to the landfill with direct leachate discharge.     

Removal of polycyclic aromatic hydrocarbons and linear alkylbenzene sulfonates from domestic wastewater in pilot constructed wetlands and a gravel filter

Removal efficiencies of polycyclic aromatic compounds (PAHs) and linear alkyl benzene sulfonates (LAS) were evaluated in a pilot-scale constructed wetland (CW) system combining a free water surface wetland, a subsurface wetland and a gravel filter in parallel. The effect of parameters such as temperature and mass loading rate was also examined. The subsurface constructed wetland system was found to have the overall best performance on pollutants removal. In particular, the average removal of PAHs and LAS was 79.2% and 55.5% for the SSF (Subsurface Flow) constructed wetland, 68.2% and 30.0% for the FWS (Free Water Surface) constructed wetland and 73.3% and 40.9% for the gravel filter, respectively. Removal efficiency and the estimated first-order volumetric removal rate constant (k_v) for both PAHs and LAS decreased with increasing water temperature. The experimental results suggest that the absorption in solid media is the main mechanism for xenobiotics removal in constructed wetlands and that the overall performance of the SSF wetland is significantly better than the FWS wetland or the gravel filter.     

人工湿地的氮去除机理

湖泊等水环境的富营养化给人类带来诸多损害,如环境、生态和经济等方面的损害。富营养化的原因和控制途径引起了包括中国在内的很多国家的关注。我国针对水环境的富营养化问题开展了大量的工作。氮是引发水环境富营养化的主要营养物之一。外源氮负荷（分点源和非点源两部分）是水环境污染负荷的重要组成部分。传统污水处理技术应用于收集系统欠缺的非点源污染的治理时成本过高。人工湿地是有效削减水环境中外源氮负荷的重要技术手段,在处理非点源污染源带来的氮负荷时更是如此。人工湿地具有氮去除效果好、耐冲击负荷能力强、投资低和生态环境友好等优点。因此人工湿地非常适合于水环境富营养化的防治。阐明人工湿地中氮的去除机理对水环境的富营养化等具有重要的意义。防渗人工湿地的氮去除机理主要包括挥发、氨化、硝化／反硝化、植物摄取和基质吸附。未防渗的人工湿地中,周围水体与人工湿地的氮交换影响着人工湿地中氮的去除。一般情况下,人工湿地中硝化／反硝化是最主要的氮去除机理。pH值小于7．5时,氨挥发可忽略。pH值在9．3以上时,氨挥发很显著。处理生活污水的人工湿地中氮的去除主要是依靠微生物的硝化／反硝化作用。在进水负荷低、气候适宜、植物物种适宜和收割频率与时机适宜的条件下,植物收割可能成为主要的去氮途径。人工合理导向的湿地的氮去除效果通常优于天然湿地。合理的设计（填料的搭配、植物物种的配置以及布水和集水的优化）对人工湿地系统中氮去除的改善有重要影响。合理的运行,如有效的水位控制,正确的植物培育、合理的植物收割等,能有效地改善湿地中的氮去除。     

山东省花生主产区土壤和花生籽粒中邻苯二甲酸酯的分布特征

在山东省四大花生主产区采集耕层土壤(0～20 cm)和花生籽粒,应用气相色谱测定样品中美国国家环保署(EPA)优先控制的6种邻苯二甲酸酯(PAEs)化合物的含量.结果表明: 山东省花生主产区土壤中6种PAEs化合物累计(∑PAEs)含量范围为0.34～2.81 mg·kg^-1,平均含量为1.22 mg·kg^-1;四大花生主产区土壤∑PAEs含量为：鲁中南山区＞鲁西平原＞胶东半岛＞鲁北平原;与美国土壤PAEs控制标准相比,山东省四大花生主产区土壤中的邻苯二甲酸正二丁酯(DBP)超标严重.花生籽粒中∑PAEs含量范围为0.17～0.66 mg·kg^-1,平均含量为0.34 mg·kg^-1,低于美国和欧洲的建议指标,健康风险很小.邻苯二甲酸二(2-乙基己基)酯(DEHP)和DBP在土壤和花生籽粒中占∑PAEs的百分比、检出率均较高,是主要的污染物组分.覆膜种植模式下土壤和花生籽粒中的∑PAEs显著高于露地种植模式.花生籽粒和土壤中的∑PAEs、DBP及DEHP存在显著正相关性,Pearson相关系数分别为0.786、0.747和0.511.     

人工湿地对抗生素复合污染的净化效果及微生物群落响应

为研究人工湿地对氟喹诺酮类(FQs)、磺胺类(SFs)、四环素类(TCs)抗生素的净化性能及微生物群落的响应,以运行多年的单层及多层(3层、6层)基质结构的水平潜流入工湿地为对象,分别采用固相萃取-高效液相色谱法和高通量测序来检测抗生素含量和微生物菌落结构,分析对比分层结构湿地系统中3类8种抗生素的去除规律、对常规污染...     

抚仙湖窑泥沟人工湿地的除磷效果研究

为了减缓和控制抚仙湖局部湖湾水体富营养化趋势,在抚仙湖北岸建设了净化面积1 hm²的人工湿地.综合利用生物氧化塘、水平潜流人工湿地和表面流人工湿地治理技术,对入湖河道窑泥沟污水中磷的去除效果进行了试验研究.结果表明,该人工湿地系统对磷具有较强的去除能力.总磷去除率在57.7%～81.10%之间,平均去除率为54.9%.单位面积磷滞留量平均为26 mg·m^-2·d^-1,其中,湿地植物同化作用磷滞留量为26.1 mg·m^-2·d^-1,约占磷滞留总量的10%,大部分磷去除是通过基质吸附和沉降作用,但主要湿地植物水芹的季节变化对相应功能区的除磷效果会产生一定影响.试验期间,各功能区单位面积磷滞留量依次为水平潜流人工湿地＞生物氧化塘＞沉淀池＞表面流人工湿地.     

模拟人工湿地中植物多样性配置对硝态氮去除的影响

为检验植物多样性对人工湿地脱氮功能的影响,在模拟人工湿地试验系统中设置了植物单种和混种处理并定期供给氮形态仅为硝态氮的模拟污水。结果表明:混种系统的出水硝态氮浓度显著低于单种(P<0.05);混种与单种系统在基质氮含量和植物氮积累量上无统计差异;质量平衡分析表明混种促进系统反硝化强度;菩提子单种系统中的硝态氮移除能力显著高于香蒲、芦苇和菖蒲单种系统,后3种硝态氮移除能力则无显著差异。本研究可为人工湿地选择高效物种、多样性配置以提高氮去除率提供依据。     

地膜使用年限对遵义市烟田土壤和烟叶邻苯二甲酸酯累积的影响

研究地膜使用年限对土壤和烟叶邻苯二甲酸酯(PAEs)积累的影响,以明确地膜持续使用条件下PAEs的土壤污染分布特征及在烟叶中的富集状况.在遵义市连阡村和沙湾村采集了不同覆膜年限的烟田土壤及相应的烟叶,采用气相色谱仪质谱联用技术(GC-MS),对土壤-烟叶中6种优先控制PAEs含量进行了测定.结果表明: 所有土壤和烟叶样品中6种邻苯二甲酸酯化合物累计(∑PAEs)分别为(2.66±0.60)和(3.58±0.64) mg·kg^-1,其中,邻苯二甲酸二(2-乙基己)酯(DEHP)含量最高,邻苯二甲酸正二丁酯(DBP)次之,二者之和分别占土壤和烟叶∑PAEs的92.7%和88.9%.DEHP、DBP、邻苯二甲酸二乙酯(DEP)和邻苯二甲酸丁基苄基酯(BBP)检出率均为100.0%,邻苯二甲酸二甲酯(DMP)的检出率略低,邻苯二甲酸正二辛酯(DnOP)检出率最低.随着地膜使用年限的增加,土壤和烟叶中PAEs含量显著增加,且在地膜使用的前1~ 8年增加更为明显,后期趋于平缓.土壤和烟叶中的PAEs含量与覆膜年限呈显著正相关关系,覆膜年限的增加会显著促进土壤和烟叶中PAEs的积累.烟叶与土壤之间∑PAEs的累积量相关性不显著.     

Determination of PAEs in soil of municipal wards of Patna,India by microwave assisted extraction and LC-MS/MS

Phthalic Acid Esters (PAEs) have become ubiquitous in environment due to unrestrained manufacture and use of plasticizers. The occurrence of PAEs in food, beverages, environmental and biological samples has been reported worldwide. PAEs are widely used in plasticizers for imparting flexibility and are not covalently bonded with the polymers, enabling PAEs to leach out due to change in pH and temperature. This study attempts to identify and quantify the PAEs in soil of Patna, India. Soil samples were collected from 22 municipal wards of Patna, Bihar. Microwave-Assisted Extraction (MAE) technique was applied for the extraction of PAEs followed by LC-MS/MS with electrospray ionization for the identification of different PAEs. Mono(4-pentenyl)phthalate (M(4P)P), Bis(2-hydroxyethyl) phthalate (BHEP), 2-Methylbutyl benzyl Phthalate (MBBP), Octyl Decyl phthalate (ODP), Heptadecyl trimethylsilyl phthalate (HDTMP), Magnesium phthalate (MgP), Diethyl Phthalate (DEP) and Dibutyl phthalate (DBP) were identified by LC-MS/MS. Interestingly, it was observed that soil samples of nine municipal wards were contaminated with high levels of maximum number PAEs identified in the study. Conclusively, the assessment of PAEs in soils samples is imperative for the management of environmental pollution generated by human activity.     

Biodegradation of phthalic acid esters (PAEs) in soil bioaugmented with acclimated activated sludge

The degradation characteristics of four phthalic acid esters (PAEs), i.e. di-methyl phthalate (DMP), di-ethyl phthalate (DEP), di-n-butyl phthalate (DBP) and di-n-octyl phthalate (DOP) in the soil augmented with acclimated sludge was investigated in order to assess the efficacy of bioaugmentation as a strategy for remediating PAEs-contaminated soil and correlate the degradation rate of PAEs with their alkyl chain length. The results demonstrated that PAEs with shorter alkyl chain, that is, DMP and DEP could be degraded more quickly than DBP and DOP. The degradation of four PAEs in the soil conformed to a first-order reaction kinetic equation. The half-lives of PAEs degradation decreased significantly with increasing carbon number of the alcohol moiety. Half-lives decreased from 2.29 days for DMP to 28.4 days for DOP when the carbon number of alkyl chain increased from one for DMP to eight for DOP. The degradation rate of PAEs and the corresponding half-lives could correlate with the alkyl chain length and their octanol–water partition coefficients (K_ow) quite well for the four PAEs tested in this study.     

城市污泥中邻苯二甲酸酯(PAEs)的厌氧微生物降解

邻苯二甲酸酯(PAEs)是城市污泥中普遍存在的一类具有内分泌干扰性作用的有机污染物.研究污泥厌氧生物处理过程中PAEs的微生物降解对保障污泥农用的安全性十分必要.本文以污泥中两种主要的PAEs——邻苯二甲酸二丁酯(DBP)和邻苯二甲酸(2-乙基己)酯(DEHP)为研究对象,通过比较PAEs在污泥厌氧消化系统与发酵产氢系统中降解过程的差异及系统污泥特性的变化,分析不同污泥厌氧生物处理系统中影响PAEs降解的可能因素.结果表明: 在污泥厌氧发酵系统中,DBP在6 d内降解率达99.6%, DEHP在整个14 d的培养期间也降解了46.1%;在发酵产氢系统中,在14 d培养过程DBP的降解率仅为19.5%,DEHP则没有明显的降解.与厌氧消化系统相比,PAEs在发酵产氢系统中的降解受到明显抑制,这与发酵产氢过程中微生物量下降、革兰氏阳性菌/革兰氏阴性菌(G⁺/G^-)和真菌/细菌变小及挥发性脂肪酸(包括乙酸、丙酸及丁酸)浓度升高有关.     

Comparison of heavy metal accumulation in a natural wetland and constructed wetlands receiving acid mine drainage

Metal accumulations in sediments and plants of constructed and natural wetlands were compared in two wetlands constructed by the Tennessee Valley Authority (TVA) for the treatment of acid mine drainage and a natural wetland. Load rates and removal efficiencies of most metals were generally greater in the constructed wetlands than in the natural wetland. There were similar sediment and plant metal concentrations between one constructed wetland and the natural wetland and greater metal concentrations in the sediments and plants in the other constructed wetland compared to the natural wetland. Data indicate that Mn, Zn, Cu, Ni, B, and Cr are being accumulated in the plants at all three wetlands, although accumulation of metals by these plants accounts for only a small percentage of the removal of the annual metal load supplied to each wetland.     

Treatment of high-strength wastewater in tropical constructed wetlands planted with Sesbania sesban: Horizontal subsurface flow versus vertical downflow

Treatment of various types of wastewaters is an urgent problem in densely populated areas of many tropical countries. We studied the potential of using Sesbania sesban, an N₂-fixing shrub, in constructed wetland systems for the treatment of high-strength wastewater. A replicated horizontal subsurface flow system and a saturated vertical downflow system was established with planted and unplanted beds to assess the effects of system design and presence of plants on treatment performance. The systems were loaded with a mixture of domestic and pig farm wastewater at three hydraulic loading rates of 80, 160 and 320 mm d^?1. The S. sesban plants grew very well in the constructed wetland systems and produced 17.2–20.2 kg dry matter m^?2 year^?1 with a high nitrogen content. Mass removal rates and removal rate constants increased with loading rate, but at 320 mm d^?1 the effluent quality was unacceptable and hydraulic problems appeared. Mass removal rates and removal rate constants were much higher than reported in other studies probably because of the high-strength wastewater, the high loading rates and the tropical conditions. Planted systems removed pollutants much more efficiently than the unplanted controls. Direct plant uptake constituted only up to 8% of the total-N removal and 2% of the P removal at the lowest loading rate, and was quantitatively of low importance compared to other removal processes. The significant effects of plants were therefore related more to their indirect effects on the removal processes. This study for the first time documents that S. sesban can be used in constructed wetland systems for the treatment of polluted water while at the same time producing a valuable N rich biomass that can be used for animal fodder or soil amendment.     

Increasing ibuprofen degradation in constructed wetlands by bioaugmentation with gravel containing biofilms of an ibuprofen‐degrading Sphingobium yanoikuyae

The aim of this study was to investigate the removal of ibuprofen in laboratory scale constructed wetlands. Four (planted and unplanted) laboratory‐scale horizontal subsurface flow constructed wetlands were supplemented with ibuprofen in order to elucidate (i) the role of plants on ibuprofen removal and (ii) to evaluate the removal performance of a bioaugmented lab scale wetland. The planted systems showed higher ibuprofen removal efficiency than an unplanted one. The system planted with Juncus effusus was found to have a higher removal rate than the system planted with Phalaris arundinacea. The highest removal rate of ibuprofen was found after inoculation of gravel previously loaded with a newly isolated ibuprofen‐degrading bacterium identified as Sphingobium yanoikuyae. This experiment showed that more than 80 days of CW community adaptation for ibuprofen treatment could be superseded by bioaugmentation with this bacterial isolate.     

Design and performance of a pilot-scale constructed wetland treatment system for natural gas storage produced water

To test the hypothesis that water produced from natural gas storage wells could be treated effectively by constructed wetland treatment systems, a modular pilot-scale system was designed, built, and used for treating gas storage produced waters. Four simulated waters representing the range of contaminant concentrations typical of actual produced waters were treated, and the system's performance was monitored. Freshwater wetland cells planted with Schoenoplectus californicus and Typha latifolia were used to treat fresh and brackish waters. Saline and hypersaline waters were treated by saltwater wetland cells planted with Spartina alterniflora and by reverse osmosis. Effective removal of cadmium, copper, lead, and zinc was achieved by the pilot-scale system. Results suggest that use of specifically designed constructed wetland treatment systems provides a flexible and effective approach for treating gas storage produced waters over a wide range of compositions.     

烟草幼苗根系分泌自毒物质种类及PAEs对根系抗氧化性能的影响

采用GC-MS技术鉴定水培烟草Burley及K326在幼苗期不同生长阶段的根系分泌物;并用不同浓度邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异辛酯(DIOP)溶液浇灌盆栽烟草幼苗,研究其根系抗氧化性能变化。结果如下:(1)Burley根系分泌物主要有3类化合物,其中自毒物质邻苯二甲酸酯(PAEs)在二叶龄期、四叶龄期、六叶龄期的相对含量分别为7.6%、0.3%、未检出;而K326根系分泌物主要有9类化合物,PAEs在二叶龄期、四叶龄期、六叶龄期的相对含量分别为35.6%、51.3%、2.2%。(2)浓度高于0.1 mmol/L的PAEs使根中超氧阴离子自由基产生的速率显著(P0.05)增加;随着DIOP及DBP浓度的增加,超氧化物歧化酶、过氧化氢酶活性增加,在0.5 mmol/L时达到最大,然后随着处理浓度的增加而下降。丙二醛的浓度随着这两种PAEs处理浓度的增加而增大。结果表明:烟草根系分泌的自毒物质PAEs达到0.5 mmol/L时,能降低根系的抗氧化性能,造成根尖细胞膜系统的氧化损伤,引起根吸收功能等一系列生理生化变化,并最终表现出自毒作用。     

Effects of three phthalate esters on the life-table demography of freshwater rotifer <Emphasis Type="Italic">Brachionus calyciflorus</Emphasis> Pallas

Phthalate esters (PAEs) are mainly used in the polymer industry as external plasticizers in PVC, and tend to migrate slowly out of the plastic, either into the air by volatilization or into water or other solvents by dissolution. Di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP) and di-2-ethylhexyl phthalate (DEHP) are three members of PAEs, identified as priority controlled hazardous substances by the United States Environmental Protection Agency, and have been shown to have potential for endocrine disrupting effects on vertebrates and humans. The effects of DBP, BBP and DEHP on survival and reproduction of the freshwater rotifer Brachionus calyciflorus were studied using life-table demographic methods. The results showed that all the life-table demographic parameters of B. calyciflorus were markedly affected by DBP and BBP, but not by DEHP. The net reproductive rate representing the output of reproduction was more affected than all the other parameters representing population growth, development or survival of the rotifers. Compared to the solvent control, DBP and BBP, both at 500 μg l⁻¹, significantly increased the net reproductive rate, and prolonged the generation time and the life expectancy at hatching of the rotifers. DBP at 50 μg l⁻¹ markedly decreased the intrinsic rate of population increase of the rotifers, but the reverse was true for BBP at 50 and 500 μg l⁻¹. Among all the parameters, the intrinsic rate of population increase was the most sensitive to DBP and BBP. The levels of PAEs in water from all the studied rivers and lakes in the world did not affect the population growth of rotifers.     

Anaerobic degradation of phthalic acid esters during digestion of municipal solid waste under landfilling conditions

Anaerobic microorganisms in municipal solid waste samples from laboratory-scale landfill reactors and a pilot-plant biogas digestor were investigated with the aim of assessing their ability to transform four commercially used phthalic acid esters (PAEs) and phthalic acid (PA). The PAEs studied were diethyl phthalate (DEP), butylbenzyl phthalate (BBP), dibutyl phthalate (DBP) and bis(2-ethylhexyl) phthalate (DEHP). No biological transformation of DEHP could be detected in any of the experiments. Together with waste samples from the simulated landfilling conditions, the PAEs (except DEHP) were hydrolytically transformed to their corresponding monoesters. These accumulated as end products, and in most cases they were not further degraded. During incubation with waste from the biogas digestor, the PAEs (except DEHP) were completely degraded to methane and carbon dioxide. The influence of the landfill development phase on the transformations was investigated utilizing PA and DEP as model substances. We found that during both the intense and stable methanogenic (but not the acidogenic) phases, the microoganisms in the samples had the potential to transform PA. A shorter lag phase was observed for the PA transformation in the samples from the stable methanogenic phase as compared with earlier phases. This indicates an increased capacity to degrade PA during the aging phases of the municipal solid waste in landfills. No enhancement of the DEP transformation could be observed as conditions in the methanogenic landfill model changed over a year's time. The results indicate that microorganisms developing in a methanogenic landfill environment have a substantially lower potential to degrade PAEs compared with those developing in a biogas reactor.Abbreviations BBP butylbenzyl phthalate - DEHP bis(2-ethylhexyl) phthalate - CoA coenzyme A - DBP dibutyl phthalate - DEP diethyl phthalate - DS dry solids - MBeP monobenzyl phthalate - MBuP monobutyl phthalate - MEP monoethyl phthalate - MSW municipal solid waste - PA phthalic acid - PAE(s) phthalic acid ester(s) - VFA volatile fatty acids