One-step synthesis of Pt-Nd co-doped Ti/SnO2-Sb nanosphere electrodes used to degrade nitrobenzene.

Ti/SnO2-Sb electrodes possess high catalytic activity and efficiently degrade nitrobenzene (NB); however, their low service life limits their wide application. In this study, we used one-step hydrothermal synthesis to successfully prepare Pt-Nd co-doped Ti/SnO2-Sb nanosphere electrodes. Scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were applied to characterize the surface morphology, microstructure, and chemical composition of the electrodes, respectively. The electrochemical activity and stability of the electrodes were characterized via linear sweep and cyclic voltammetry, electrochemical impedance spectroscopy, and an accelerated service life test; their performance for NB degradation was also studied. An appropriate amount of Pt-Nd co-doping refined the average grain size of SnO2 and formed a uniform and compact coating on the electrode surface. The oxygen evolution potential, total voltammetric charge, and electron transfer resistance of the Ti/SnO2-Sb-Nd-Pt electrodes were 1.88 V, 3.77 mC/cm2, and 11.50 Ω, respectively. Hydroxy radical was the main active radical species during the electrolytic degradation of nitrobenzene with Ti/SnO2-Sb-Nd-Pt. After Pt-Nd co-doping, the accelerated service life of the electrodes was extended from 8.0 min to 78.2 h (500 mA/cm2); although the NB degradation rate decreased from 94.1 to 80.6%, the total amount of theoretical catalytic degradation of NB in the effective working time increased from 17.4 to 8754.1 mg/cm2. These findings reveal good application potential for the electrodes and provide a reference for developing efficient and stable electrode materials.

Synthesis and evaluation of Mn-Sn modified Ru-Ir electrode for electrocatalytic treatment of high chloride acrylonitrile wastewater.

Acrylonitrile wastewater was an organic wastewater with strong toxicity and poor biodegradability. Therefore, electro-catalytic technology became a promising acrylonitrile wastewater treatment technology because of no secondary pollution, wide application range and low water quality requirements. The optimal Mn-Sn modified Ru-Ir electrode material was synthesized by thermal method and applied in electro-catalytic treatment of acrylonitrile wastewater. The electrode materials were characterized by SEM, TEM, XRD, XPS and electrochemical characterization. SEM, TEM, XRD and XPS indicated that Mn and Sn were capable of incorporating and replacing the part of Ru or Ir and could alter the microstructure of Ru-Ir and the types of Mn and Sn oxides, raising the oxygen evolution potential (OEP) and voltampere charge. When the molar ratio of Mn-Sn was 1:1, OEP, voltampere charge and exchange current density could reach 1.303 V, 1.51 C/cm2 and 6.29×10-4 A/cm2, respectively. The co-doping of Mn-Sn had significant influence on the electrocatalytic performance of Ru-Ir electrode materials. The optimum synthesis conditions of Mn-Sn modified Ru-Ir electrode were as follows: the molar ratio of Mn-Sn was 1:1, calcination time was 4.0 hours, calcination temperature was 450℃, and solvent was water. Under certain conditions, the removal rate of acrylonitrile with Mn-Sn modified Ru-Ir electrode was 100%. Mn-Sn modified Ru-Ir electrode had high oxygen evolution potential and good removal effect of acrylonitrile, which was higher than that of ruthenium iridium electrode and RuO2 electrode.

Preparation and evaluation of Pd-Sn modified Ru-Ir electrode for denitrification of high chlorine ammonia-nitrogen wastewater.

In this paper, Pd-Sn modified Ru-Ir electrode was prepared by thermal oxidation method, and the effects of doping amount of Pd-Sn and synthesis conditions on Pd-Sn modified Ru-Ir electrode performance were studied. Linear sweep voltammetry(LSV), cyclic voltammetry(CV), and the Tafel curve were used to study the electrochemical performance of the Pd-Sn modified Ru-Ir electrode materials. The effects of the doping amount of Pd-Sn on the microstructure and valence states of Pd-Sn modified Ru-Ir electrode materials were investigated by SEM, TEM, XRD, and XPS. When the mass of Pd-Sn accounted for 1.5% of the total mass of the elements, the molar ratio of Ru-Ir was 2:1, and the molar ratio of Pd-Sn was 3:1; the LSV, CV, and the Tafel curves indicated that Pd-Sn modified Ru-Ir electrode had the lowest chlorine evolution potential (1.0640 V vs. SCE), the best CV curve coincidence, and the smallest corrosion current density (6.5 × 10-4 A/cm2), showing the best chlorine evolution performance, the best durability, and corrosion resistance; the characterization of SEM, TEM, XRD, and XPS showed that Pd-Sn was successfully doped into Ru-Ir electrode materials; the crystallinity of Pd-Sn modified Ru-Ir electrode was the highest, and the binding energy was the lowest, but the crystal form of Ru-Ir solid solution did not have changed. The optimal synthesis conditions of Pd-Sn modified Ru-Ir electrode material were as follows: Pd-Sn molar ratio was 3:1, calcination temperature was 500 ℃, calcination time was 4 h, and water was used as solvent. Pd-Sn modified Ru-Ir electrode can efficiently treat high chlorine ammonia-nitrogen wastewater, when the reaction volume was 200 mL, the initial concentration of NH3-N was 100 mg/L, the concentration of chloride ion was 5000 mg/L, the current was 0.75 A, and the reaction time was 40 min; the removal rate of ammonia nitrogen can reach 100%.Responsible editor: Weiming Zhang.

Bioremediation of intertidal zones polluted by heavy oil spilling using immobilized laccase-bacteria consortium.

Heavy oil pollution in the intertidal zones has become a worldwide environmental problem. In this study, bioremediation on heavy oil pollutants in the intertidal zones using an immobilized laccase-bacteria consortium system was evaluated with the aid of intertidal experimental pools built in the coastal area. It is found that degradation efficiency of the immobilized laccase-bacteria consortium for heavy oil was 66.5% after 100 days remediation, with the reaction rate constant of 0.018 d-1. Gas Chromatograph-Mass Spectrometer analysis shows that degradation efficiency of saturated hydrocarbons and aromatic hydrocarbons were 79.2% and 78.7%, which were 64.9% and 65.1% higher than control. It is further seen that degradation of long-chain n-alkanes of C26-C35 and polycyclic aromatic hydrocarbons with more than three rings were significant. Metagenomic analysis indicates that the immobilized laccase-bacterial consortium has not only increased the biodiversity of heavy oil degrading bacteria, but also accelerated the degradation of heavy oil.

Isolation and niche characteristics in simultaneous nitrification and denitrification application of an aerobic denitrifier, Acinetobacter sp. YS2.

The ecological niche of aerobic denitrifiers in activated sludge is little studied, but this determines the performance of these bacteria in reactors. Acinetobacter sp. YS2 isolated from a treatment process for petrochemical wastewater and showed excellent nitrogen removal performance. In the nitrification and denitrification process, the removal efficiencies of NH4+-N and NO3--N were 87.81% and 88.20% at 24 h, respectively, and nitrogen balance analysis indicated that the proportions of nitrogen removal by gaseous nitrogen were 37.58% and 46.45%, respectively. During simultaneous nitrification and denitrification (SND) treatment of synthetic petrochemical wastewater in a sequencing batch reactor (SBR), aerobic denitrifiers became the dominant species and the proportion reached 87.44% in the microbial community. The removal efficiencies of NH4+-N and TN were 99.46% and 80.36% over 5 days, respectively. This research has shown that aerobic denitrifiers can become the dominant species in the applications of SND treatment for petrochemical wastewater.

In situ fabrication of I-doped Bi2O2CO3/g-C3N4 heterojunctions for enhanced photodegradation activity under visible light.

Iodine-doped Bi2O2CO3/g-C3N4 heterojunctions consisting of graphitic carbon nitride (g-C3N4) and iodine-doped bismutite (Bi2O2CO3) components were successfully in situ synthesized by a one-pot hydrothermal method. Characterizations such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) demonstrated iodine was favorably doped into the Bi2O2CO3 component, of which the {001} facets grew in situ from {002} facets of g-C3N4 for the heterostructure construction of I-doped Bi2O2CO3/g-C3N4 (IB/CN). The photocatalytic activity of catalysts was evaluated by the degradation efficiency of 1,5-dihydroxynaphthalene under visible light. 1.5-IB/CN with a reasonable iodine doping amount (Bi: I molar ratio = 1.0: 1.5) exhibited the superior photodegradation performance compared to Bi2O2CO3, achieving an 85.5% removal ratio after 100 min illumination. The enhanced activity of 1.5-IB/CN was attributed to both of the heterostructure that promoted the separation of photoinduced carriers and iodine doping that tuned the bandgap for sufficient visible-light harvesting. The degradation intermediates of 1,5-dihydroxynaphthalene in the system were determined and its possible photodegradation pathway was proposed in detail. This study provides a rational approach for enhancing the visible-light catalytic activity of wide-bandgap Bi2O2CO3, and reveals a new perspective on the removal mechanism of organic pollutants.

Aerobic denitrifiers with petroleum metabolizing ability isolated from caprolactam sewage treatment pool.

To improve the biological nitrogen removal efficiency of petrochemical wastewater, three aerobic denitrifiers were isolated from caprolactam sewage treatment pool. They were identified as Acinetobacter sp. YY1, Sphingomonas sp. YY2 and Pseudomonas sp. YY3, respectively. The nitrification and denitrification enzyme genes could be detected using polymerase chain reaction (PCR). Moreover, the strain YY2 was a novel aerobic denitrifier belongs to genus of Sphingomonas, which showed great ability for metabolizing aromatic hydrocarbons. In the nitrification and denitrification process, the total nitrogen (TN) removal efficiency after 48 h was 94.22% and 90.10%, respectively. In the process of simultaneous nitrification and denitrification in mixed N-source, ammonia nitrogen was preferentially utilized. Furthermore, the strain YY2 exhibited excellent extracellular polymer secretion properties and excellent aerobic denitrification capacity using petroleum refractory organic compounds, which are beneficial for the formation of bacterial micelles and the engineering applications for the treatment of petrochemical wastewater.

A comprehensive evaluation of re-circulated bio-filter as a pretreatment process for petroleum refinery wastewater.

Conventional biological treatment process is not very efficient for the treatment of petroleum refinery wastewater (PRW) that contains high-concentration of organic contaminants. Prior to biological treatment, an additional pretreatment process for PRW is required for the effluent to meet the discharge standards. While re-circulated bio-filter (RBF) has been applied as a pretreatment process in several PRW treatment plants, its effects have not been comprehensively evaluated. In this study, the parameters of operation, the changes in pollution indexes and contaminant composition in an engineered RBF have been investigated. We found that mainly highly active de-carbonization bacteria were present in the RBF, while no nitrification bacteria were found in the RBF. This indicated the absence of nitrification in this process. The biodegradable organic contaminants were susceptible to degradation by RBF, which decreased the Biological Oxygen Demand (BOD5) by 83.64% and the Chemical Oxygen Demand (CODCr) by 54.63%. Consequently, the alkalinity and pH value of RBF effluent significantly increased, which was unfavorable for the control of operating parameters in subsequent biological treatment. Along with the decrease of CODCr, the RBF effluent exhibited a reduction in biodegradability. 834 kinds of recalcitrant polar organic contaminants remained in the effluent; most of the contaminant molecules having complex structures of aromatic, polycyclic and heterocyclic rings. The results of this study showed that RBF could efficiently treat PRW for biodegradable organic contaminants removal; however, it is difficult to treat bio-refractory organic contaminants, which was unfavorable for the subsequent biological treatment process operation. An improved process might provide overall guarantees for the PRW treatment.

Vapor intrusion risk of lead scavengers 1,2-dibromoethane (EDB) and 1,2-dichloroethane (DCA).

Vapor intrusion of synthetic fuel additives represented a critical yet still neglected problem at sites impacted by petroleum fuel releases. This study used an advanced numerical model to simulate the vapor intrusion risk of lead scavengers 1,2-dibromoethane (ethylene dibromide, EDB) and 1,2-dichloroethane (DCA) under different site conditions. We found that simulated EDB and DCA indoor air concentrations can exceed USEPA screening level (4.7 × 10(-3) µg/m(3) for EDB and 1.1 × 10(-1) µg/m(3) for DCA) if the source concentration is high enough (is still within the concentration range found at leaking UST site). To evaluate the chance that vapor intrusion of EDB might exceed the USEPA screening levels for indoor air, the simulation results were compared to the distribution of EDB at leaking UST sites in the US. If there is no degradation of EDB or only abiotic degradation of EDB, from 15% to 37% of leaking UST sites might exceed the USEPA screening level. This study supports the statements made by USEPA in the Petroleum Vapor Intrusion (PVI) Guidance that the screening criteria for petroleum hydrocarbon may not provide sufficient protectiveness for fuel releases containing EDB and DCA. Based on a thorough literature review, we also compiled previous published data on the EDB and DCA groundwater source concentrations and their degradation rates. These data are valuable in evaluating EDB and DCA vapor intrusion risk. In addition, a set of refined attenuation factors based on site-specific information (e.g., soil types, source depths, and degradation rates) were provided for establishing site-specific screening criteria for EDB and DCA. Overall, this study points out that lead scavengers EDB and DCA may cause vapor intrusion problems. As more field data of EDB and DCA become available, we recommend that USEPA consider including these data in the existing PVI database and possibly revising the PVI Guidance as necessary.

Effects of adding bulking agent, inorganic nutrient and microbial inocula on biopile treatment for oil-field drilling waste.

Contamination from oil-field drilling waste is a worldwide environmental problem. This study investigated the performance of four bench-scale biopiles in treating drilling waste: 1) direct biopile (DW), 2) biopile plus oil-degrading microbial consortium (DW + M), 3) biopile plus microbial consortium and bulking agents (saw dust) (DW + M + BA), 4) biopile plus microbial consortium, bulking agents, and inorganic nutrients (Urea and K2HPO4) (DW + M + BA + N). Ninety days of biopiling removed 41.0%, 44.0%, 55.7% and 87.4% of total petroleum hydrocarbon (TPH) in the pile "DW", "DW + M", "DW + M + BA", and "DW + M + BA + N" respectively. Addition of inorganic nutrient and bulking agents resulted in a 56.9% and 26.6% increase in TPH removal efficiency respectively. In contrast, inoculation of hydrocarbon-degrading microorganisms only slightly enhanced the contaminant removal (increased 7.3%). The biopile with stronger contaminant removal also had higher pile temperature and lower pile pH (e.g., in "DW + M + BA + N"). GC-MS analysis shows that biopiling significantly reduced the total number of detected contaminants and changed the chemical composition. Overall, this study shows that biopiling is an effective remediation technology for drilling waste. Adding inorganic nutrients and bulking agents can significantly improve biopile performance while addition of microbial inocula had minimal positive impacts on contaminant removal.

Sensitivity and uncertainty analysis for Abreu & Johnson numerical vapor intrusion model.

This study conducted one-at-a-time (OAT) sensitivity and uncertainty analysis for a numerical vapor intrusion model for nine input parameters, including soil porosity, soil moisture, soil air permeability, aerobic biodegradation rate, building depressurization, crack width, floor thickness, building volume, and indoor air exchange rate. Simulations were performed for three soil types (clay, silt, and sand), two source depths (3 and 8m), and two source concentrations (1 and 400 g/m(3)). Model sensitivity and uncertainty for shallow and high-concentration vapor sources (3m and 400 g/m(3)) are much smaller than for deep and low-concentration sources (8m and 1g/m(3)). For high-concentration sources, soil air permeability, indoor air exchange rate, and building depressurization (for high permeable soil like sand) are key contributors to model output uncertainty. For low-concentration sources, soil porosity, soil moisture, aerobic biodegradation rate and soil gas permeability are key contributors to model output uncertainty. Another important finding is that impacts of aerobic biodegradation on vapor intrusion potential of petroleum hydrocarbons are negligible when vapor source concentration is high, because of insufficient oxygen supply that limits aerobic biodegradation activities.

Catalytic ozonation of petroleum refinery wastewater utilizing Mn-Fe-Cu/Al2O 3 catalyst.

There is of great interest to develop an economic and high-efficient catalytic ozonation system (COS) for the treatment of biologically refractory wastewaters. Applications of COS require options of commercially feasible catalysts. Experiments in the present study were designed to prepare and investigate a novel manganese-iron-copper oxide-supported alumina-assisted COS (Mn-Fe-Cu/Al2O3-COS) for the pretreatment of petroleum refinery wastewater. The highly dispersed composite metal oxides on the catalyst surface greatly promoted the performance of catalytic ozonation. Hydroxyl radical mediated oxidation is a dominant reaction in Mn-Fe-Cu/Al2O3-COS. Mn-Fe-Cu/Al2O3-COS enhanced COD removal by 32.7% compared with a single ozonation system and by 8-16% compared with Mn-Fe/Al2O3-COS, Mn-Cu/Al2O3-COS, and Fe-Cu/Al2O3-COS. The O/C and H/C ratios of oxygen-containing polar compounds significantly increased after catalytic ozonation, and the biodegradability of petroleum refinery wastewater was significantly improved. This study illustrates potential applications of Mn-Fe-Cu/Al2O3-COS for pretreatment of biologically refractory wastewaters.