Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M). Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction. Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs. C@M shows efficient catalytic degradation of pollutants over a wide pH range. Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.     

Comparison of CNT-PVA membrane and commercial polymeric membranes in treatment of emulsified oily wastewater

CNT-PVA membrane was fabricated and compared with polymeric membranes. The separation performance was evaluated by homemade and cutting fluid emulsions. The three membranes show similar oil retention rates. CNT-PVA membranes have higher permeation fluxes compared with polymeric membranes. CNT-PVA membrane shows higher fouling resistance. Membrane separation is an attractive technique for removal of emulsified oily wastewater. However, polymeric membranes which dominate the current market usually suffer from severe membrane fouling. Therefore, membranes with high fouling resistance are imperative to treat emulsified oily wastewater. In this study, carbon nanotube-polyvinyl alcohol (CNT-PVA) membrane was fabricated. And its separation performance for emulsified oily wastewater was compared with two commercial polymeric membranes (PVDF membrane and PES membrane) by filtration of two homemade emulsions and one cutting fluid emulsion. The results show that these membranes have similar oil retention efficiencies for the three emulsions. Whereas, the permeation flux of CNT-PVA membrane is 1.60 to 3.09 times of PVDF membrane and 1.41 to 11.4 times of PES membrane, respectively. Moreover, after five consecutive operation circles of filtration process and back flush, CNT-PVA membrane can recover 62.3% to 72.9% of its initial pure water flux. However, the pure water flux recovery rates are only 24.1% to 35.3% for PVDF membrane and 6.0% to 26.3% for PES membrane, respectively. Therefore, CNT-PVA membrane are more resistant to oil fouling compared with the two polymeric membranes, showing superior potential in treatment of emulsified oily wastewater.     

Enhanced activation of peroxymonosulfate by CNT-TiO2 under UV-light assistance for efficient degradation of organic pollutants

CNT-TiO₂ composite is used to activate PMS under UV-light assistance. Superior performance is due to the enhanced electron-transfer ability of CNT. SO₄•⁻, •OH and ¹O₂ play key roles in the degradation of organic pollutants. In this work, a UV-light assisted peroxymonosulfate (PMS) activation system was constructed with the composite catalyst of multi-walled carbon nanotubes (CNT) - titanium dioxide (TiO₂). Under the UV light irradiation, the photoinduced electrons generated from TiO₂ could be continuously transferred to CNT for the activation of PMS to improve the catalytic performance of organic pollutant degradation. Meanwhile, the separation of photoinduced electron-hole pairs could enhance the photocatalysis efficiency. The electron spin resonance spectroscopy (EPR) and quenching experiments confirmed the generation of sulfate radical (SO₄•⁻), hydroxyl radical (•OH) and singlet oxygen (¹O₂) in the UV/PMS/20%CNT-TiO₂ system. Almost 100% phenol degradation was observed within 20 min UV-light irradiation. The kinetic reaction rate constant of the UV/PMS/20%CNT-TiO₂ system (0.18 min⁻¹) was 23.7 times higher than that of the PMS/Co₃O₄ system (0.0076 min⁻¹). This higher catalytic performance was ascribed to the introduction of photoinduced electrons, which could enhance the activation of PMS by the transfer of electrons in the UV/PMS/CNT-TiO₂ system.     

Long-Term Operation of a Biofilter for Simultaneous Removal of H2S and NH3

Abstract

Simultaneous removal of NH₃ and H₂S was investigated using two types of biofilters—one packed with wood chips and the other with granular activated carbon (GAC). Experimental tests and measurements included analyses of removal efficiency (RE), metabolic products, and results of long-term operation (around 240 days). The REs for NH₃ and H₂S were 92 and 99.9%, respectively, before deactivation. After deactivation, the RE for NH₃ and H₂S were decreased to 30–50% and 75%, respectively. The activity of nitrifying bacteria was inhibited by high concentrations of H₂S (over 200 ppm) but recovered gradually after H₂S addition was ceased. However, the Thiobacillus thioparus as sulfur oxidizing bacteria did not show inhibition at the NH₃ concentration under 150-ppm conditions. The deactivation of the biofilter was caused by metabolic products [elemental sulfur and (NH₄)₂SO₄] ac-cumulating on the packing materials during the extended operation. The removal capacities for NH₃ and H₂S were 6.0–8.0 and 45–75 mg N, S/L/hr, respectively.     

Enantioselectivity of racemic metolachlor and S-metolachlor in maize seedlings

Chiral herbicides may have enantioselective effects on plants. In this study, we assessed and compared the enantioselectivity of the chiral herbicides rac-metolachlor and S-metolachlor to maize seedlings. The superoxide dismutase activity (SOD) activity of roots and stem leaves treated by rac-metolachlor was 1.38 and 1.99 times that of roots and stem leaves treated by S-metolachlor. The peroxidase activity (POD) activity of roots and stem leaves was 1.48 and 2.79 times that of roots and stem leaves treated by S-metolachlor, respectively, while the catalase activity (CAT) activity was 4.77 and 8.37 times greater, respectively. The Hill reaction activity of leaves treated by rac-metolachlor were 1.45, 1.33, and 1.14 times those treated by S-metolachlor with treatments of 18.6, 37.2, and 74.4 μM. The differences observed between treatments of rac- and S-metolachlor were significant. Significant differences in maize seedling morphology were also observed between rac- and S-metolachlor treatments. The degradation rate of S-metolachlor in roots was greater than that of rac-metolachlor. The half-lives of rac- and S-metolachlor were 80.6 and 60.3 h at 18.6 μM; 119.5 and 90 h at 37.2 μM; and 169 and 164.8 h at 74.4 μM, respectively. Using the liquid chromatography-mass spectrometry method, hydroxymetolachlor, deschlorometolachlor and deschlorometolachlor propanol were considered to be possible metabolites. We determined the enantioselective toxicity of rac- and S-metolachlor to maize and speculated on the proposed metabolic pathway of metolachlor in maize roots. These results will help to develop an understanding of the proper application of rac- and S-metolachlor in crops, and give some information for environmental safety evaluation of rac- and S-metolachlor.     

Characteristics and management of domestic waste in a rural area of the Tibetan Plateau

In the rural area of the Tibetan Plateau (RATP), the characteristics of domestic waste, people’s environmental awareness, people’s willingness to pay and their influence factors were firstly studied by questionnaires, field samplings and laboratory tests. The results showed that, in the RATP, the generation of domestic waste was 85 g?d-1 per capita and it was mainly composed of plastics, inert waste, kitchen waste, glass and paper. The waste bulk density, moisture content, ash, combustible and low calorific value were 65 kg?m-3, 19.25%, 44.90%, 35.85% and 10,520 kJ?kg-1 respectively. These characteristics are influenced by income sources and geographical position to some extent. Classified collection should be promoted widely on the household and the village basis. Compost, fermentation, landfill, bioreactor landfill and semi-aerobic landfill have been approved as effective techniques to treat domestic waste, except incineration. The distance of 50–800 m between each collection facility and the disposal fee of around $0.8 per month per household are suggested. For suburbs or large population villages, it’s better to treat domestic waste by the centralized way. But for the remote rural areas, a decentralized way is proposed. Significantly, the educational and economic influence should be considered into an effective domestic waste management program.

Implications:?The current situatio n of the environment in the rural areas of the Tibetan Plateau (RATP) was surveyed. There, the generation of organics and moisture of domestic waste were low but ash, recyclables, and combustibles were high. People’s knowledge of domestic waste was absent but their participation in management was strong. Based on the current situation, compost, fermentation, and landfill were effective but incineration was inappropriate. Also, a localized mini landfill for a cluster of villages and or settlements was the best method there.     

Risk assessment for safety of soils and vegetables around a lead/zinc mine

Concentrations of heavy metals (Pb, Zn, Cd, Cu) were determined in soils and vegetables (chrysanthemum, spinach and four cultivars of Chinese cabbage from the area adjacent to a Pb/Zn mine in Shaoxing, Zhejiang province, China, and compared with the Chinese National Standards for Soil Environmental Quality. The accumulation of heavy metals in cabbage cv. Siyuegreen was investigated at different distances from the center of the mine. The vegetable plantation soils were polluted with Pb, Cd, Cu and Zn, especially by Pb and Cd. The levels of Pb and Cd were 20 and 30 times higher than the permitted standards, indicating that this Pb/Zn mining area is unsuitable for agricultural use. Chinese cabbage, chrysanthemum and spinach had different enrichment coefficients. The enrichment coefficient of Cd from soil to roots of chrysanthemum was >80% and from roots to leaves of cabbage cv. Shanghaigreen was >120%. These vegetables were polluted by heavy metals and could not be regarded as safe for human consumption. Environmental accumulation of heavy metals in the vegetable plantation soils was proportional to heavy metal accumulation in vegetables and both were inversely proportional to the distance from the lead/zinc mine.     

炼油废水污泥脱水工艺条件的优化

采用化学除油降黏—污泥调理—离心脱水工艺处理某炼油厂废水处理系统的混合污泥,并对工艺条件进行优化。实验结果表明,最佳的工艺条件为：化学除油降黏阶段处理体系的pH=4,反应温度35 ℃,H₂O₂加入量 2 g/L,m（H₂O₂）∶ m（Fe²⁺）=4,反应时间 60 min;污泥调理反应阶段的CaO加入量7.0 g/L;离心脱水阶段在分离因数为1 558时脱水5 min。在此条件下,得到的泥饼的含水率为70.0%~75.0%（w）,含油率小于2%（w）,污泥比阻约为3.0×10⁷ s²/g。     

Mussel isotope signature as indicator of nutrient pollution in a freshwater eutrophic lake: species, spatial, and seasonal variability

Stable nitrogen isotope ratios of five mussel species from littoral and pelagic areas were investigated with different trophic states in the eutrophic Lake Taihu, the third largest lake in China. Interpopulation variability for these mussels was relatively small in foot tissues because of the slow turnover time. Seasonal and spatial variations among the δ ¹⁵N values of mussels might be due in part to the natural variation in δ ¹⁵N values of potential food sources and the variation in the amount of human pollutions discharged into various locations of the lake. Although the increase of mussel δ ¹⁵N values was accompanied by the increase of nutrient concentrations in most situations in this study, statistically significant correlations were only 22% of the total correlations in this survey, which might be attributed to the different time-scale variations in nutrient concentrations and isotope signatures and the unknown details of the trophic pathways and metabolism for incorporation of these nutrients.     

Impact of carbon source on nitrous oxide emission from anoxic/oxic biological nitrogen removal process and identification of its emission sources

Wastewater treatment is an important source of nitrous oxide (N₂O), which is a strong greenhouse gas and dominate ozone-depleting substance. The purpose of this study was to evaluate the effect of carbon source on N₂O emission from anoxic/oxic biological nitrogen removal process. The mechanisms of N₂O emission were also studied. Long-term experiments were operated to evaluate the effect of three different carbon sources (i.e., glucose, sodium acetate, and soluble starch) on N₂O emission characteristics. And batch experiments, in the presence or absence of specific inhibitors, were carried out to identify the sources of N₂O emission. The ammonia-oxidizing bacteria (AOB) and denitrifiers community compositions under different circumstances were also analyzed based on which the underlying mechanisms of N₂O emission were elucidated. The conversion ratios of N₂O in reactors with glucose, sodium acetate, and soluble starch were 5.3 %, 8.8 %, and 2.8 %, respectively. The primary process responsible for N₂O emission was nitrifier denitrification by Nitrosomonas-like AOB, while denitrification by heterotrophic denitrifiers acted as the sink. Reactor with sodium acetate showed the highest N₂O emission, together with the highest nitrogen and phosphate removal ratios. Carbon source has a significant impact on N₂O emission quantity and relatively minor effect on its production mechanism.