纳米二氧化钛光催化氧化油田采出水中萘和芴的影响因素分析

利用纳米二氧化钛光催化氧化技术,分析了不同影响因素UV波长(UVA 365 nm、UVB 308 nm和UVC 254nm)、温度、p H、催化剂(Ti O2)、抑制剂(Bu OH)和氧化剂(O2、H2O2和O3)对油田采出水中多环芳烃萘和芴降解效率的影响,并进一步优化出单因子的最佳条件。实验结果表明,各因素对萘和芴降解有不同的影响,但其效果都随波长减小和酸度降低而得到增强。当其他条件为一致最优时(T=90℃,Ti O2=0.5 g/L和Bu OH=0.03 mol),当H2O2=0.01 mol或O2=30 m L/min时,萘的降解率最高,而当H2O2=0.1 mol或O3=30 m L/min对芴的降解效果最好。     

g-C3N4/TiO2复合薄膜光催化降解石油采出水中多环芳烃

针对亟待解决的石油开采废水中的多环芳烃(polycyclic aromatic hydrocarbons,PAHs)污染物的生物毒害性问题,利用紫外光辐照g-C₃N₄/TiO₂复合薄膜光催化剂,对取自内蒙某采油现场的采出水水样进行降解处理,研究多组分PAHs污染物共存条件下的不同环数PAHs发生光催化氧化反应的降解规律及降解动力学。采用扫描电子显微镜(scanning electron microscope,SEM)表征光催化剂表面微观形貌,采用固相微萃取法富集和萃取水样中的PAHs,采用气相色谱-质谱联用法(gas chromatography-mass spectrometry,GC-MS)检测分析PAHs含量。经UV/gC₃N₄/TiO₂光催化反应处理,采出水中不溶的颗粒态萘优先于溶解态萘被降解去除,经60 min后对萘的总去除率可达61.13%。大于4环不溶性高环PAHs,可被优先光催化降解,从而高毒性的PAHs污染物被逐级转化为相对较低生物毒性的...     

UV-Fenton催化氧化法对采油废水中多环芳烃的处理效果

针对采油废水中含有多环芳烃种类多且较难去除的特点,采用UV-Fenton技术对采油废水中多环芳烃的处理效果进行了研究,通过正交实验和单因素实验,研究了在254 nm波长紫外光照射下,Fe2+投加量、H2O2投加量、pH值和光照时间对水样中多环芳烃中的菲和芴处理效果的影响。实验结果显示,处理初始浓度为1 000μg/L的菲、芴时,反应的最佳工艺条件为:Fe2+浓度为1.8 mmol/L、H2O2投加量为0.15 mmol/L、pH值为4、光照时间1.25 h。在此条件下,菲和芴的去除率可达71.9%。     

固废拆解场污染土壤中多环芳烃降解菌的筛选鉴定与降解特性

以腐植酸(HA)溶液为吸附剂、从受多环芳烃污染的土壤中分离出来的降解菌制成为生物修复剂,以多环芳烃(PAHs)萘、菲、芘、荧蒽、苯并蒽、苯并芘为土壤污染物,对PAHs污染土壤进行修复实验。目的是筛选与分离吸附于HA的PAHs降解菌,研究HA与降解菌的协同效应对PAHs的降解效率的影响。用经过HA吸附的PAHs富集分离培养出1株高效降解菌株,命名为Tzyx3,鉴定其为解脂耶氏酵母菌(Yarrowia lipolytica)。15 d后,土壤中萘、菲、芘、荧蒽、苯并蒽、苯并芘的降解率分别为90.7%、91.0%、74.7%、86.9%、84.7%和74.7%,表明Tzyx3和HA在PAHs污染土壤中存在协作关系,Tzyx3能够直接利用HA对土壤中的多环芳烃进行降解。     

一株芴降解菌的分离鉴定及其对多环芳烃的降解广谱性研究

从某焦化厂活性污泥中筛选出一株芴的优势降解菌株W-1,经形态学观察、生理生化实验和16S rDNA基因序列分析,确定W-1为粪产碱杆菌.在接种量10%(V/V),初始芴浓度40 mg/L,pH 7.0,温度30℃的条件下,接种培养11 d后,菌株W-1对芴的降解效率达到87.8%.菌株W-1对多环芳烃的降解具有广谱性,...     

紫外光照处理低浓度萘普生废水

萘普生为水体中常见的一种非甾体药物类污染物。以300W汞灯为光源,研究紫外光照降解法对于含低浓度萘普生废水的处理效果,发现pH对萘普生光解效果有直接影响,降解优异性顺序为酸性>碱性>中性。通过实验,确定了萘普生光解的最佳pH值为4,光照时间为40 min,在该实验条件下,萘普生的降解率达到97.6%。通过液相色谱-质谱联用法对降解后水样进行检测,初步推导出光解中间产物为6-甲氧基-2-乙酰基萘、6-甲氧基-2-乙烯萘及β-萘酚。     

降解菌对堆肥中多环芳烃降解作用的研究

通过在堆肥中加入经过驯化的降解菌这种土壤有机污染生物修复技术 ,对堆肥中多环芳烃的浓度变化进行监测 ,从而了解降解菌对堆肥中多环芳烃的降解作用。实验结果表明 ,降解菌的加入能明显地提高多环芳烃的降解率 ,本次实验中 ,菲、芴的去除率提高了 2 5 %左右 ,芘的去除率提高了约 4 5 %。     

降解菌对堆肥中多环芳烃降解作用的研究

通过在堆肥中加人经过驯化的降解菌这种土壤有机污染生物修复技术，对堆肥中多环芳烃的浓度变化进行监测，从而了解降解菌对堆肥中多环芳烃的降解作用。实验结果表明，降解菌的加人能明显地提高多环芳烃的降解率，本次实验中，菲、芴的去除率提高了25％左右，芘的去除率提高了约45％。     

木糖氧化无色杆菌及混合菌群对多环芳烃的降解特性

采用木糖氧化无色杆菌及混合菌降解水中多环芳烃。考察了木糖氧化无色杆菌的降解广谱性及其对多环芳烃混合底物的降解,特别考察了混合菌对具有弱致癌性的■(Chrysene)的降解特性。结果表明,木糖氧化无色杆菌具有较宽的降解谱,对多环芳烃混合底物具有良好降解特性。当蒽、菲、芘和■4种PAHs共存时,木糖氧化无色杆菌对蒽、菲、芘和■的降解效率分别达83%、66%、85%和80%。与单一木糖氧化无色杆菌相比,混合菌对的降解效率较高。尖镰孢菌与木糖氧化无色杆菌、茄镰孢菌与木糖氧化无色杆菌和3株菌同时共存时,■的降解效率分别达87%、88%和86%。     

粉煤灰井下填充时PAHs对地下水环境的影响

模拟平煤集团矸石电厂以及焦煤集团演马电厂粉煤灰井下填充过程,设计了静态浸泡和动态淋溶实验,并以固相萃取-气相色谱/质谱联用方法,测定了溶出液中的16种多环芳烃含量.实验结果表明:溶出液中主要的PAHs物质是萘、苊、芴、菲、蒽,均为4环以下的多环芳烃类物质,其含量较低,其中菲和蒽的总含量较高,说明在粉煤灰井下填充过程中,多环芳烃类污染物能够从粉煤灰中迁移至水体,并对地下水环境造成一定的影响.     

Photolysis of polycyclic aromatic hydrocarbons adsorbed on spruce [Picea abies (L) Karst] needles under sunlight irradiation

Photolysis of polycyclic aromatic hydrocarbons (PAHs) sorbed on surfaces of spruce [Picea abies (L.) Karst.] needles under sunlight irradiation was investigated. PAHs were produced by combustion of polyvinyl chloride (PVC), wood, high-density polyethylene (HDPE), and styrene in a stove. The factors of sunlight irradiation on the surfaces of spruce needles were taken into consideration when investigating the kinetic parameters. The photolysis of the 18 PAHs under study follows first-order kinetics. The photolysis half-lives range from 15 h for dibenzo(a,h)anthracene to 75 h for phenanthrene. Photolysis of some PAHs on surfaces of spruce needles may play an important role on the fate of PAHs in the environment.     

Disappearance of polycyclic aromatic hydrocarbons sorbed on surfaces of pine [Pinua thunbergii] needles under irradiation of sunlight: Volatilization and photolysis

The solar photodegradation of 16 polycyclic aromatic hydrocarbons (PAHs), sorbed on surfaces of pine [Pinua thunbergii] needles was investigated. The PAHs were produced by combustion of polystyrene and exposed onto the surfaces of pine needles. The disappearance of PAHs sorbed on the pine needle surfaces is mainly caused by volatilization and photolysis, with photolysis playing a major role. The volatilization rates correlate with PAH molecular weight significantly. The photolysis of the 16 PAHs follows first-order kinetics and their photolysis half-lives (t_1/2,P) range from 12.9 h for naphthalene to 65.4 h for fluorene. The PAHs have similar half-lives whether they are sorbed on spruce or pine needles. Compared with water, the cuticular waxes of pine needles can stabilize photolysis of PAHs and facilitate accumulation of PAHs. t_1/2,P for selected PAHs correlate with semi-empirically calculated energy of the highest occupied orbital (E_HOMO). Photochemical behaviors of PAHs are dependent not only on their molecular structures but also the physical–chemical properties of the substrate on which they are adsorbed.     

Behavior and prediction of photochemical degradation of chlorinated polycyclic aromatic hydrocarbons in cyclohexane

The photochemical degradation of 11 chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and the corresponding 5 parent PAHs was examined to simulate the compound’s fate on aerosol surfaces. All the ClPAHs and PAHs decayed according to the first-order reaction rate kinetics. The photolysis rates of ClPAHs varied greatly according to the skeleton of PAHs; the rates of chlorophenanthrenes (ClPhes) and 1-chloropyrene were higher than those of corresponding parent PAHs, whereas chlorofluoranthenes, 7-chlorobenz[a]anthracene and 6-chlorobenzo[a]pyrene were more stable under irradiation compared to respective parent PAH. Considering the photoproducts of ClPhes detected, the oxidation could occur immediately at positions of the highest frontier electron density. Finally, the quantitative structure-property relationship models were developed for direct photolysis half-lives and average quantum yields of the ClPAHs and parent PAHs, in which the significant factors affecting photolysis were E_LUMO+1, total energy and surface area, and E_LUMO, E_LUMO − E_HOMO and total energy, respectively.     

Photolysis of PAHs in aqueous phase by UV irradiation.

The photooxidation of polycyclic aromatic hydrocarbons (PAHs) was investigated in an aqueous ethanolic solution irradiated with a medium-pressure mercury lamp in laboratory photoreactors equipped with a quartz immersion well. Degradation photolysis of fluorene was more efficient than sensitized photolytic oxidation in the presence of TiO2 suspensions. Photolysis kinetics was dependent on molecular weight and the presence and type of substituents. During the photolytic degradation of fluorene and its derivatives, 9-fluorenone and its corresponding derivatives, which were more resistant to photolysis, were formed.     

Stigmastane and hopanes as conserved biomarkers for estimating oil biodegradation in a former refinery plant-contaminated soil

In the last decade, a refinery plant located in Lido Adriano, East Ravenna (Italy) has been subject to mineral oil contamination. The mineral crude oil, extracted from the offshore in Adriatic sea, consisted of 78% aliphatics, cyclic alkanes and saturated polycyclic hydrocarbons, 9% aromatics, polycyclic aromatic hydrocarbons (PAHs) and alkylated derivatives, and 13% of tars/asphaltenes. Analysis of soil after 10 years of natural attenuation revealed a complete depletion of linear (n-C(9)-C(24)), light aromatics (C1-C3/benzenes) and PAHs (C2/naphthalene, C1/phenanthrene); besides a substantial degradation of isoprenoids prystane and phytane, branched and cyclic alkanes. The remaining contaminants which withstood to natural degradation was saturated polycyclic hydrocarbons (perhydro-PAH derivatives), unsaturated polycyclic hydrocarbons (tetrahydro, dihydro-PAH derivatives), terpanes, steranes and unidentified compounds. Such residues resulted in 80% reduction of its concentration after two months of laboratory treatment. Samples were extracted by organic solvents, separated by silica/alumina gel column chromatography and analyzed by gas chromatography-mass selective detector (GC-MSD). Identification and quantification of aliphatic, cyclic alkanes, typical PAHs, terpanes and steranes were carried out to chromatograms of M/Z=85, 83, individual M/Zs, M/Z=191 and 217, respectively. The present work shows that, among numerous biomarkers present in the source oil, stigmastane and two isomers of hopane showed invariable concentrations after laboratory experiments that mimic natural biodegradation in the field, so they can be used as conserved internal biomarkers. These are very useful tools to assess alterations in less stable classes of saturated compounds contained in petroleum. Marked degradation of perhydro, tetrahydro, dihydro-PAH derivatives in the laboratory treatment has been evidenced.     

A comparative study on the uptake of polycyclic aromatic hydrocarbons by Anodonta californiensis

Uptake of polycyclic aromatic hydrocarbons (PAHs) by the freshwater bivalve mollusc Anodonta californiensis was examined in the presence and absence of surfactant in order to gain further insight into mixture toxicity and to predict whether certain mixtures have negative and/or positive effects on aquatic organisms. In the presence of surfactant, the uptake of anthracene or chrysene was higher than that of naphthalene, given the same concentration in the solution. In the absence of surfactant, the trend was similar, but the uptakes were increased by approximately 100% compared to those in the presence of surfactant. On the uptake of naphthalene, the presence of anthracene showed only minor influence. The uptake of anthracene was affected by both naphthalene and chrysene. The uptake of chrysene was influenced by neither naphthalene nor anthracene. There was no observable displacement of divalent cations from the surface of the gill membrane by any of the PAHs studied.     

Reductive hydrogenation of polycyclic aromatic hydrocarbons catalyzed by metalloporphyrins

The hydrogenation of polycyclic aromatic hydrocarbons (PAHs) (naphthalene, anthracene, and phenanthrene) catalyzed by metalloporphyrins based on cobalt, nickel or iron was studied in aqueous solutions at room temperature and ambient pressure. Nickel porphyrin (P1) activated by nanosized zero-valent iron (nano-ZVI) and cobalt porphyrins (P2) and (P4) activated by titanium(III) citrate as the electron donor were demonstrated to be promising catalysts for the reductive hydrogenation of PAHs. In particular, partially saturated di-, tetra-, and octahydrogenated products were obtained for anthracene or phenanthrene using a nickel porphyrin activated by nano-ZVI, while naphthalene was transformed to tetralin. Systems containing cobalt porphyrins activated by titanium(III) citrate exhibited a high selectivity and activity toward hydrogenation of anthracene, producing 9,10-dihydroanthracene. However, no formation of hydrogenated hydrocarbons was observed from naphthalene or phenanthrene using cobalt porphyrins.     

Immobilization of fungal laccase onto a nonionic surfactant-modified clay material: application to PAH degradation

Nonionic surfactant-modified clay is a useful absorbent material that effectively removes hydrophobic organic compounds from soil/groundwater. We developed a novel material by applying an immobilized fungal laccase onto nonionic surfactant-modified clay. Low-water-solubility polycyclic aromatic hydrocarbons (PAHs) (naphthalene/phenanthrene) were degraded in the presence of this bioactive material. PAH degradation by free laccase was higher than degradation by immobilized laccase when the surfactant concentration was allowed to form micelles. PAH degradation by immobilized laccase on TX-100-modified clay was higher than on Brij35-modified clay. Strong laccase degradation of PAH can be maintained by adding surfactant monomers or micelles. The physical adsorption of nonionic surfactants onto clay plays an important role in PAH degradation by laccase, which can be explained by the structure and molecular interactions of the surfactant with the clay and enzyme. A system where laccase is immobilized onto TX-100-monomer-modified clay is a good candidate bioactive material for in situ PAHs bioremediation.