Reductive degradation of nitrobenzene in aqueous solution by zero-valent iron

The reductive degradation of nitrobenzene (NB) by zero-valent iron was investigated. Experimental results showed that the degradation of NB was influenced by pH and NB concentration. The optimum pH value was found to be 3.0 for the reductive degradation of NB in the tested pH ranges of 3.0-12.0. The formation rate of aniline, a major reductive product of NB, followed zero-order kinetics at various pH levels. Furthermore, GC/MS analysis showed that aniline, azobenzene and azoxybenzene were the reductive products of NB by zero-valent iron. With the analysis of the products with GC/MS and FTIR, possible reductive pathways of NB by zero-valent iron were suggested.     

The study of distribution and fate of nitrobenzene in a water/sediment microcosm

In November 2005, an explosion occurred at a petrochemical plant of the Jilin Petrochemical Corporation in Jilin Province, China. A nearby water body was seriously polluted with a large spill of toxic substances made up of a mixture of benzene, aniline, and nitrobenzene (NB). To understand the long term impact of NB on public health and ecosystem around the Songhua River, it was necessary to investigate its fate in the environment. In this study, a microcosm was used to mimic the polluted water system and to study the transport and fate of NB in the river water body. The volatility and biodegradation of NB was investigated and a Markov model was applied to predict the fate of NB in the environment. The simulated results matched very well with the results obtained from the microcosm experiment. The model indicated that at room temperature and after around 500 h, there was only residual NB in the water and sediment. Most of the NB (around 82%) evaporated into the air and 18% was degraded by microorganisms.     

Tolerance, uptake and removal of nitrobenzene by a newly-found remediation species Mirabilis jalapa L

The growth, photosynthesis rate, and ultrastructure of Mirabilis jalapa L. as a newly-found remediation species under stress of nitrobenzene (NB) and its uptake and removal of NB by the plants were investigated. The results showed that M. jalapa plants could endure contaminated soils by lower than 10.0 mg NB kg⁻¹ because there was no decrease in the total length of the plant roots, the maximum length of the hypocotyle, the length of the first seminal root, the height of the shoots and the dry biomass of the seedlings as well as the photosynthesis rate of the plants compared with those in the control. In particular, the growth of the plants could be significantly (P < 0.01) enhanced by 0.1 mg NB kg⁻¹ under unautoclaved and autoclaved soils. Ultrastructural observations on leaf cells of the plants found that these cells had smooth, clean and continuous cell membranes and cell walls, indicating that there was no obvious damage by NB in comparison with those in the control. Although the absorption of NB in shoots and roots of M. jalapa was weak, plant-promoted biodegradation of NB was considerable and the dominant contribution in the removal of NB from contaminated soils, suggesting the feasibility of M. jalapa applied to phytoremediation of NB contaminated soils.     

硝基苯对硫酸盐还原过程的影响

为了探明硝基苯(NB)对硫酸盐还原的影响,揭示相关过程机制,采用以丙酸盐为碳源和电子供体的序批式厌氧反应系统(水力停留时间为33 h),考察了碳硫比为0.63～5.0,NB浓度为2.5～50 mg/L条件下,系统的硫酸盐还原效能。研究结果表明,NB对硫酸盐还原过程存在抑制作用,当系统NB进水浓度低于30 mg/L时,NB对硫酸盐还原过程抑制并不显著,但当进水NB浓度达50 mg/L时,硫酸盐还原率由近100%迅速降至17%。对比实验结果进一步表明,NB初始浓度为16.5 mg/L条件下,硫酸盐的比还原速率和丙酸的比消耗速率分别为对照组的63%和52%。硫酸盐还原的抑制主要源自NB及其还原产物苯胺(AN)的生物毒性,但上述抑制作用可逆。     

Enhancing the performance of sequencing batch reactors by adding crushed date seeds to remove high concentrations of 2,4-dinitrophenol

Wastewater treatment systems using simultaneous adsorption and biodegradation processes have been successful in treating toxic pollutants present in industrial wastewater. The goal of this investigation was to assess the effectiveness of date seeds in reducing the toxic effects of 2,4-dinitrophenol (DNP) on activated sludge microorganisms. Two identical sequencing batch reactors (SBRs) (4-L glass vessel), each with a 3.5-L working volume, were used. The initial DNP concentrations in the reactor were 50, 75, 100, 250, and 500 mg/L. The reactor amended with date seeds was capable of degrading DNP at significantly greater rates (11 +/- 2.5 mg/L x h) than the control SBR (4 +/- 1.2 mg/L x h) at a 95% confidence level. Date seeds can be added to the mixed liquor of activated sludge treatment plants to remove high concentrations of DNP from wastewater, to protect the treatment plant against toxic components in the influent and enhance the settling characteristics of the mixed liquor.     

零价铁与厌氧微生物协同还原地下水中的硝基苯

通过间歇式实验,考察了零价铁与厌氧微生物协同还原地下水中硝基苯的效果。实验结果表明,由零价铁腐蚀为厌氧微生物提供H2电子供体还原硝基苯的效果明显优于零价铁和微生物单独作用,硝基苯去除率分别提高21.8%和57.0%。弱酸性条件有利于协同反应进行,当初始pH为5.0和6.0时,4 d后硝基苯去除率比初始pH为7.0时的提高74.4%和35.2%。增加零价铁投加量可提高协同还原的效果,零价铁最佳投加量为250 mg/L。零价铁腐蚀产生的Fe2+无法作为电子供体被微生物利用,但可作为无机营养元素促进协同过程。由于零价铁产H2速率受表面覆盖物影响不明显,在地下水修复过程中可保证协同效果并延长零价铁的使用寿命。     

Reduction of nitrobenzene with sulfides catalyzed by the black carbons from crop-residue ashes

In this paper, three types of black carbons (BCs) named R-BC, W-BC, and C-BC were derived from rice straw ashes, wheat straw ashes, and corn straw ashes, respectively. Under room temperature and in an anaerobic aqueous solution, these three types of BCs could catalyze the reduction of nitrobenzene (NB) by sulfides rather than only act as the superabsorbent. The catalytic activities of BCs derived from different crop-residue ashes were very different and in the order of R-BC > W-BC > C-BC, since the reaction rate constants (k _obs) of NB with the BCs in the presence of 3 mM sulfides were 0.0186, 0.0063, and 0.0051 h^?1, respectively. The key catalytic active sites for NB reduction were evaluated, with four types of modified BCs and two types of tailored graphite as the model catalysts. The results indicated that BCs probably had two types of active sites for NB reduction, the microscopic graphene moieties and the surface oxygen functional groups. Since the sulfides and BCs often coexist in the environment, this BC-catalyzed reduction technology of NACs may be applied as an in situ remediation technique without the need for reagent addition.     

A sequential zero valent iron and aerobic biodegradation treatment system for nitrobenzene

The remediation of nitroaromatic contaminated groundwater is sometimes difficult because nitroaromatic compounds are resistant to biodegradation and, when they do transform, the degradation of the products may also be incomplete. A simple nitroaromatic compound, nitrobenzene, was chosen to assess the feasibility of an in situ multi-zone treatment system at the laboratory scale. The proposed treatment system consists of a zero valent granular iron zone to reduce nitrobenzene to aniline, followed by a passive oxygen release zone for the aerobic biodegradation of the aniline daughter product using pristine aquifer material from Canadian Forces Base (CFB) Borden, Ontario, as an initial microbial source. In laboratory batch experiments, nitrobenzene was found to reduce quickly in the presence of granular iron forming aniline, which was not further degraded but remained partially sorbed onto the granular iron surface. Aniline was found to be readily biodegraded with little metabolic lag under aerobic conditions using the pristine aquifer material. A sequential column experiment, containing a granular iron reducing zone and an aerobic biodegradation zone, successively degraded nitrobenzene and then aniline to below detection limits (0.5 microM) without any noticeable reduction in hydraulic conductivity from biofouling, or through the formation of precipitates.     

Synthesis of nanoscale zero-valent iron/ordered mesoporous carbon for adsorption and synergistic reduction of nitrobenzene

Nanoscale zero-valent iron (NZVI) supported on ordered mesoporous carbon (OMC) was synthesized through liquid phase reduction route. The NZVI/OMC composite was characterized by X-ray diffraction, N(2) adsorption/desorption and transmission electron microscopy. Results reveal that the composite possesses ordered mesostructure with NZVI distributing homogeneously on the surface of OMC support. The removal effects of nitrobenzene (NB) in water with OMC, NZVI/OMC and non-supported NZVI were evaluated. Results indicate that NZVI/OMC shows enhanced removal efficiency, which is attributed to its adsorption and synergistic reduction for NB. The transformation process of NB was further investigated by HPLC. Nitrosobenzene and phenylhydroxylamine were detected as intermediate products and aniline was the final reductive product.     

Study of inclusion complex of beta-cyclodextrin and nitrobenzene

beta-cyclodextrin can react with nitrobenzene to form an inclusion complex which is characterized by (1)H NMR and powder X-ray diffractometry. The ratio of beta-CD to NB in inclusion complex is determined as 1:1. At 25 degrees C, the dissociated constant, K(D), of the inclusion complex is measured as 6.5 x 10(-3) M in neutral solution (pH=7.0), but in alkali (pH=13.5), K(D) is 3.2 x 10(-2) M which is much larger than that measured in neutral.     

Reduction of nitrobenzene in groundwater by iron nanoparticles immobilized in PEG/nylon membrane

The highly reactive iron nanoparticles (NPs) immobilized in nylon membrane were synthesized and characterized, and the reduction of nitrobenzene (NB) in groundwater by the NPs was investigated. Environmental scanning electron microscopy (ESEM) images showed that the NPs distributed homogeneously on the membrane surface without agglomeration. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the NPs immobilized in membrane were mainly composed of Fe-oxides rather than zero-valent iron. Thermogravimetric (TG) analysis suggested that the weight percentage of the immobilized NPs and the oxygen introduced to the reacted sample after 80min reaction were about 18.5% and 13%, respectively. Moreover, Fourier transform infrared (FTIR) analysis further demonstrated the changes on the membrane surface after thermal grafting, NPs immobilizing and reacting for 80min. Using the reactive NPs immobilized in nylon membrane, NB in groundwater was rapidly and quantitatively decreased by 68.9% just in the first 20min, the Fe(2+) associated with the iron NPs immobilized in PEG/nylon66 membrane was mainly responsible for this reduction. The reaction appeared to follow pseudo-first-order kinetics and the rate constants increased upon decreasing the pH value. The samples we prepared exhibited good corrosion resistance for humic acid (HA) but had a short-term performance for NB degradation. More so, the groundwater chemistry had a negative influence on the reactivity of membrane immobilized NPs.     

产酸克雷伯氏菌Klebsiella oxytoca对硝基苯及4-氯硝基苯的降解

硝基苯类化合物生物降解菌的筛选及性能研究，是制药、染料等行业废水达标的重要基础。以浓度梯度升高法筛选到一株硝基苯厌氧降解菌Klebsiella oxytoca NBA-1。考察了该菌对氧气的需求，以及在厌氧条件下，温度、pH值、外加葡萄糖及硝基苯初始浓度等环境因子对菌株降解硝基苯能力的影响，并进一步讨论菌株对氯取代硝基苯类化合物的降解情况。结果表明，该菌在厌氧条件下生长比好氧条件下慢，但降解速度更快；厌氧降解硝基苯的最佳pH值和温度和分别为8．3和30～35℃；加入0．3％～0．5％的葡萄糖可促进降解，且对300mg／L以下的硝基苯均有降解能力；该菌能将4-氯硝基苯转化为4-氯苯胺，并进一步脱氯为苯胺。研究结果可为硝基苯及含氯硝基苯的处理工艺选择提供相关的参考依据。     

Membrane bioreactor treatment of commonly used organophosphate pesticides

Five pesticide formulations registered for use in Canada containing organophosphate-insecticide active ingredients azinphos-methyl, chlorpyrifos, diazinon, malathion and phorate were subjected to treatment by membrane bioreactor (MBR) technology. The target active ingredients were introduced to the MBR at ppm level concentrations. The biodegradation of these compounds was analyzed daily using selected ion monitoring gas chromatography-mass spectrometry (GC/MS-SIM) following extraction of the analytes using solid-phase extraction (SPE). Amounts measuring 83 % to 98 % of the target analytes were removed with steady-state concentrations being reached within 5 days of their introduction. The dissolved oxygen, temperature, pH, and total heterotrophic bacterial population were monitored daily to ensure optimal conditions for biodegradation. The quality of the effluent from the MBR was assessed daily through spectrophotometric methods. Measurements were conducted for the concentration of ammonia, nitrate, nitrite, total and reactive phosphorus, as well as the chemical oxygen demand (COD) of the effluent. This study demonstrated that the MBR technology is feasible and efficient for treatment of organophosphate pesticides without introducing additional chemical additives.     

Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments using delta13C and 14C measurements

Few techniques exist to measure the biodegradation of recalcitrant organic compounds such as chlorinated hydrocarbons (CHC) in situ, yet predictions of biodegradation rates are needed for assessing monitored natural attenuation. Traditional techniques measuring O2, CO2, or chemical concentrations (in situ respiration, metabolite and soil air monitoring) may not be sufficiently sensitive to estimate biodegradation rates for these compounds. This study combined isotopic measurements (14C and delta13C of CO2 and delta13C of CHCs) in conjunction with traditional methods to assess in situ biodegradation of perchloroethylene (PCE) and its metabolites in PCE-contaminated vadose zone sediments. CHC, ethene, ethane, methane, O2, and CO2 concentrations were measured over 56 days using gas chromatography (GC). delta13C of PCE, trichloroethylene (TCE) and cis-1,2-dichloroethylene (DCE), delta13C and 14C of vadose zone CO2 and sediment organic matter, and delta13C, 14C, and deltaD of methane were measured using a GC-isotope ratio mass spectrometer or accelerator mass spectrometer. PCE metabolites accounted for 0.2% to 18% of CHC concentration suggesting limited reductive dechlorination. Metabolites TCE and DCE were significantly enriched in (13)C with respect to PCE indicating metabolite biodegradation. Average delta13C-CO2 in source area wells (-23.5 per thousand) was significantly lower compared to background wells (-18.4 per thousand) indicating CHC mineralization. Calculated CHC mineralization rates were 0.003 to 0.01 mg DCE/kg soil/day based on lower 14C values of CO2 in the contaminated wells (63% to 107% modern carbon (pMC)) relative to the control well (117 pMC). Approximately 74% of the methane was calculated to be derived from in situ CHC biodegradation based on the 14C measurement of methane (29 pMC). 14C-CO2 analyses was a sensitive measurement for quantifying in situ recalcitrant organic compound mineralization in vadose zone sediments for which limited methodological tools exist.     

强化土著微生物处理硝基苯和苯胺污染地下水

以硝基苯、苯胺为主要污染物的污染地下水为研究对象,加入激活剂(乳糖、Na2HPO4、乳糖+Na2HPO4、乙醇、牛肉膏、蛋白胨)激活土著微生物,并考察其对土著微生物生长及硝基苯、苯胺降解效果的影响。加入激活剂3d后测各个水样的脱氢酶活性,对培养9d后的水样进行气相色谱/质谱(GC/MS)分析。结果表明,加入乳糖的水样中,其微生物相对增长率达157.2%,硝基苯、苯胺的相对去除率分别为14.90%和0.79%;加入Na2HPO4和乙醇的水样中,其微生物增长和硝基苯、苯胺降解情况均没有明显变化;加入乳糖+Na2HPO4的水样中,微生物相对增长率达180.3%,硝基苯、苯胺的相对去除率分别为24.20%和1.21%;加入牛肉膏的水样中,微生物的相对增长率为830.7%,硝基苯、苯胺的相对去除率分别为99.99%和99.67%;加入蛋白胨的水样中,其微生物相对增长率为686.0%,硝基苯、苯胺的相对去除率分别为99.33%和58.94%。GC/MS分析结果表明,加入激活剂后对氯苯胺、1-甲基-4-硝基苯等其他有机物的降解率均有提高。由此可见,通过激活土著微生物修复有机物污染地下水是可行的。     

Novel method for determining pyrene biodegradation using synchronous fluorimetry

To study the biodegradation rate of pyrene dissolved in liquid medium supplemented with mineral salts, a synchronous fluorimetry (SF) method was established. The limit of detection for pyrene dissolved in mineral salts medium (MSM) was determined as 0.19 ng/ml with a relative standard deviation of less than 1.3% (n = 9). The pyrene degrading rates of four bacterial strains were investigated using this method under the same experimental conditions. The degradation rates of the three active strains ranged from 76% to 87% after a 14-h incubation. The results were confirmed by the gas chromatography with a flame ionized detector (GC/FID) method. This implies that pyrene degradation can be directly monitored by the SF method without the solvent extraction of samples. The advantages of SF are that it is less laborious, faster, and less expensive than the GC/FID determination method with solvent extraction. The SF method provides a new tool for studying the degradation of polynuclear aromatic hydrocarbons (PAHs) in the natural environment and under experimental conditions.     

In vitro biodegradation of Arabian Light 250 by a marine mixed culture using fertilizers as nitrogen and phosphorous sources

The improved in vitro bioremediation of Arabian Light crude oil in synthetic sea water by a mixed culture of bacteria is reported. Effects of fish meal, meat meal 80 % proteins and sophorolipids on the biodegradation were evaluated during a three-week incubation using GC/FID and GC/MS analysis of the remaining oil. Fish meal and more particularly meat meal 80 % proteins used at 0,5 mg.ml⁻¹ involve no nitrogen and phosphorous limits when used as sole source of nutrients. Biodegradation processes in the first four days of the incubation supplemented with sophrolipids are accelerated two fold over controls.     

Biodegradation of benzene, toluene, and xylene (BTX) in liquid culture and in soil by Bacillus subtilis and Pseudomonas aeruginosa strains and a formulated bacterial consortium

Purpose

The major aromatic constituents of petroleum products viz. benzene, toluene, and mixture of xylenes (BTX) are responsible for environmental pollution and inflict serious public concern. Therefore, BTX biodegradation potential of individual as well as formulated bacterial consortium was evaluated. This study highlighted the role of hydrogen peroxide (H₂O₂), nitrate, and phosphate in stimulating the biodegradation of BTX compounds under hypoxic condition.

Materials and methods

The individual bacterium viz. Bacillus subtilis DM-04 and Pseudomonas aeruginosa M and NM strains and a consortium comprising of the above bacteria were inoculated to BTX-containing liquid medium and in soil. The bioremediation experiment was carried out for 120?h in BTX-containing liquid culture and for 90?days in BTX-contaminated soil. The kinetics of BTX degradation either in presence or absence of H₂O₂, nitrate, and phosphate was analyzed using biochemical and gas chromatographic (GC) technique.

Results

Bacterial consortium was found to be superior in degrading BTX either in soil or in liquid medium as compared to degradation of same compounds by individual strains of the consortium. The rate of BTX biodegradation was further enhanced when the liquid medium/soil was exogenously supplemented with 0.01?% (v/v) H₂O₂, phosphate, and nitrate_. The GC analysis of BTX biodegradation (90?days post-inoculation) in soil by bacterial consortium confirmed the preferential degradation of benzene compared to m-xylene and toluene.

Conclusions

It may be concluded that the bacterial consortium in the present study can degrade BTX compounds at a significantly higher rate as compared to the degradation of the same compounds by individual members of the consortium. Further, addition of H₂O₂ in the culture medium as an additional source of oxygen, and nitrate and phosphate as an alternative electron acceptor and macronutrient, respectively, significantly enhanced the rate of BTX biodegradation under oxygen-limited condition.     

The primary aerobic biodegradation of biodiesel B20

We describe the primary aerobic biodegradation of a B20 fuel (20% soybean fatty acid methyl esters, 80% petroleum diesel) by unacclimated inocula from a rainwater detention pond. Biodegradation was rapid and essentially complete, with an overall median 'half-life', at approximately 100 ppm B20, of 6.8 days (n=34). Using purge-and-trap and extraction methodologies, both coupled to GC/MS, and hexachloroethane and hexachlorobenzene as conserved internal markers in the B20, we followed the biodegradation of total detectable material, 76 individual analytes and eight undifferentiated groups of isomers, and calculated their half-lives under these conditions. The fatty acid methyl esters, n-alkanes and iso-alkanes, and simple and alkylated aromatic compounds were the most readily degraded compounds, followed by the naphthenes. The last (identified) compounds to be degraded were ethylalkanes, trisubstituted cyclohexanes and decalins, but even these disappeared with an apparent 'half-life' of <30 days.     

Assessment of five bioaccessibility assays for predicting the efficacy of petroleum hydrocarbon biodegradation in aged contaminated soils

In this study, the bioaccessibility of petroleum hydrocarbons in aged contaminated soils (1.6-67gkg(-1)) was assessed using four non-exhaustive extraction techniques (100% 1-butanol, 100% 1-propanol, 50% 1-propanol in water and hydroxypropyl-β-cyclodextrin) and the persulfate oxidation method. Using linear regression analysis, residual hydrocarbon concentrations following bioaccessibility assessment were compared to residual hydrocarbon concentrations following biodegradation in laboratory-scale microcosms in order to determine whether bioaccessibility assays can predict the endpoint of hydrocarbon biodegradation. The relationship between residual hydrocarbon concentrations following microcosm biodegradation and bioaccessibility assessment was linear (r(2)=0.71-0.97) indicating that bioaccessibility assays have the potential to predict the extent of hydrocarbon biodegradation. However, the slope of best fit varied depending on the hydrocarbon fractional range assessed. For the C(10)-C(14) hydrocarbon fraction, the slope of best fit ranged from 0.12 to 0.27 indicating that the non-exhaustive or persulfate oxidation methods removed 3.5-8 times more hydrocarbons than biodegradation. Conversely, for the higher molecular weight hydrocarbon fractions (C(29)-C(36) and C(37)-C(40)), biodegradation removed up to 3.3 times more hydrocarbons compared to bioaccessibility assays with the resulting slope of best fit ranging from 1.0-1.9 to 2.0-3.3 respectively. For mid-range hydrocarbons (C(15)-C(28)), a slope of approximately one was obtained indicating that C(15)-C(28) hydrocarbon removal by these bioaccessibility assays may approximate the extent of biodegradation. While this study demonstrates the potential of predicting biodegradation endpoints using bioaccessibility assays, limitations of the study include a small data set and that all soils were collected from a single site, presumably resulting from a single contamination source. Further evaluation and validation is required using soils from a range of hydrocarbon contamination sources in order to develop robust assays for predicting bioremediation endpoints in the field.