A comparative investigation of NdSrCu_(1-x) Co_x O_(4-δ) and Sm_(1.8) Ce_(0.2) Cu_(1-x) Co_x O_(4-δ) (x:0–0.4) for NO decomposition

A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ (x: 0–0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu 1-x Co x O 4-δ catalysts were of oxygen vacancies whereas the Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level, the oxygen vacancy density of NdSrCu 1-x Co x O 4-δ decreased while the over-stoichiometric oxygen amount of Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO 3.702 catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr -1 , and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO 3.702 NdSrCu 0.8 Co 0.2 O 3.736 NdSrCu 0.6 Co 0.4 O 3.789 Sm 1.8 Ce 0.2 Cu 0.6 Co 0.4 O 4.187 Sm 1.8 Ce 0.2 Cu 0.8 Co 0.2 O 4.104 Sm 1.8 Ce 0.2 CuO 4.045 , in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu 3+ /Cu 2+ redox ability of NdSrCu 1-x Co x O 4-δ account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.     

Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water

Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3) 3·9H2O and Co(NO3) 2·6H2O as the precursors,and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy) propionic acid(2,4-DP) ,nitrobenzene and oxalic acid.The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation eciency during the degradation of each organic pollutant,and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism.The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance.In the catalytic ozonation of 2,4-DP,the apparent reaction rate constants(k) were determined to be 1.456×10-2 min-1 for ozonation alone and 4.740×10-2 min-1 for O3/Fe3O4-CoO/Al2O3.And O3/Fe3O4-CoO/Al2O3 had a larger Rct(6.614×10-9) calculated by the relative method than O3 did(1.800×10-9) ,showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical.Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid.The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree.     

Variations between rice cultivars in iron and manganese plaque on roots and the relation with plant cadmium uptake

To understand certain mechanisms causing variations between rice cultivars with regard to cadmium uptake and tolerance, pot soil experiments were conducted with two rice cultivars of di erent genotypes under di erent soil Cd levels. The relationships between plant Cd uptake and iron/manganese (Fe/Mn) plaque formation on roots were investigated. The results showed that rice cultivars di ered markedly in Cd uptake and tolerance. Under soil Cd treatments, Cd concentrations and accumulations in the cultivar Shanyou 63 (the genotype indica) were significantly higher than those in the cultivar Wuyunjing 7 (the genotype japonica) (P < 0.01, or P < 0.05), and Shanyou 63 was more sensitive to Cd toxicity than Wuyunjing 7. The di erences between the rice cultivars were the largest at relatively low soil Cd level (i.e., 10 mg/kg). Fe concentrations in dithionite-citrate-bicarbonate root extracts of Shanyou 63 were generally lower than that of Wuyunjing 7, and the di erence was the most significant under the treatment of 10 mg Cd/kg soil. The results indicated that the formation of iron plaque on rice roots could act as a barrier to soil Cd toxicity, and may be a “bu er” or a “reservoir” which could reduce Cd uptake into rice roots. And the plaque may contribute, to some extent, to the genotypic di erences of rice cultivars in Cd uptake and tolerance.     

Modelling sulphate-enhanced cadmium uptake by Zea mays from nutrient solution under conditions of constant free Cd2+ ion activity

A controlled hydroponic experiment was undertaken to investigate Cd uptake in relation to the activity of Cd species in solution other than the free ion (Cd²⁺) by maintaining a constant Cd²⁺ activity under variable SO₄₂⁻ and Cl⁻ concentrations exposed to maize (Zea mays var. Cameron) plants. The objectives of these experiments were: (1) to distinguish and quantify the different uptake rates of free and inorganic-complexed Cd from nutrient solution, and (2) to model the uptake of Cd by maize with a Biotic Ligand Model (BLM) in a system which facilitates the close examination of root characteristics. Results of the current experiments suggest that, in addition to the free ion, CdSO₄⁰ complexes are important factors in determining Cd uptake in nutrient solution by maize plants. Higher nominal SO₄²⁻ concentrations in solution generally resulted in a greater Cd accumulation by maize plants than predicted by the Cd²⁺ activity. A better integration of the complete dataset for the 3 harvest times (6, 9 and 11 days after treatment) was achieved by including consideration of both the duration of Cd exposure and especially the root surface area to express Cd uptake. Similarly, the fit of the BLM was also improved when taking into account exposure time and expressing uptake in terms of root morphological parameters.     

Iron-doped Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO with NH3

The catalysts of iron-doped Mn-Ce/TiO 2(Fe-Mn-Ce/TiO 2) prepared by sol-gel method were investigated for low temperature selective catalytic reduction(SCR) of NO with NH 3.It was found that the NO conversion over Fe-Mn-Ce/TiO 2 was obviously improved after iron doping compared with that over Mn-Ce/TiO 2.Fe-Mn-Ce/TiO 2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity.The results showed that 96.8% NO conversion was obtained over Fe(0.1)-Mn-Ce/TiO 2 at 180°C at a space velocity of 50,000 hr 1.Fe-Mn-Ce/TiO 2 exhibited much higher resistance to H 2 O and SO 2 than that of Mn-Ce/TiO 2.The properties of the catalysts were characterized using X-ray diffraction(XRD),N 2 adsorption,temperature programmed desorption(NH 3-TPD and NOx-TPD),and Xray photoelectron spectroscopy(XPS) techniques.BET,NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping.It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe3+ state.The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts.The oxygen concentrations on the surface of the catalysts were found to increase after iron doping.Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H2 O and SO2.     

Determination of N-nitrosodimethylamine in drinking water by UPLC-MS/MS

The method for detecting N-nitrosodimethylamine (NDMA) in drinking water using ultra performance liquid chromatography (UPLC) coupled with tandem mass spectrometry (MS/MS) was improved by optimizing the clean-up procedure to remove the matrix interference in pretreatment process, and was then applied to a survey of NDMA in both raw and finished water samples from five water treatment plants in South China. The NDMA concentrations ranged from 4.7 to 15.1 ng/L in raw water samples, and from 4.68 to 46.9 ng/L in finished water. The NDMA concentration in raw water was found to be related with nitrite concentration, and during the treatment, the NDMA concentration increased following ozonation but decreased after subsequent activated carbon treatment.     

Cover crop effects on nitrous oxide emission from a manure-treated Mollisol

Agriculture contributes 40–60% of the total annual N₂O emissions to the atmosphere. Development of management practices to reduce these emissions would have a significant impact on greenhouse gas levels. Non-leguminous cover crops are efficient scavengers of residual soil NO₃, thereby reducing leaching losses. However, the effect of a grass cover crop on N₂O emissions from soil receiving liquid swine manure has not been evaluated. This study investigated: (i) the temporal patterns of N₂O emissions following addition of swine manure slurry in a laboratory setting under fluctuating soil moisture regimes; (ii) assessed the potential of a rye (Secale cereale L.) cover crop to decrease N₂O emissions under these conditions; and (iii) quantified field N₂O emissions in response to either spring applied urea ammonium nitrate (UAN) or different rates of fall-applied liquid swine manure, in the presence or absence of a rye/oat winter cover crop. Laboratory experiments investigating cover crop effects N₂O emissions were performed in a controlled environment chamber programmed for a 14 h light period, 18 °C day temperature, and 15 °C night temperature. Treatments with or without a living rye cover crop were treated with either: (i) no manure; (ii) a phosphorus-based manure application rate (low manure): or (iii) a nitrogen-based manure application rate (high manure). We observed a significant reduction in N₂O emissions in the presence of the rye cover crop. Field experiments were performed on a fine-loamy soil in Central Iowa from October 12, 2005 to October 2, 2006. We observed no significant effect of the cover crop on cumulative N₂O emissions in the field. The primary factor influencing N₂O emission was N application rate, regardless of form or timing. The response of N₂O emission to N additions was non-linear, with progressively more N₂O emitted with increasing N application. These results indicate that while cover crops have the potential to reduce N₂O emissions, N application rate may be the overriding factor.     

UV/H2O2工艺降解微囊藻毒素-LR

采用UV/H₂O₂联合工艺,研究了光强、初始浓度、H₂O₂投加量、pH及阴离子对微囊藻毒素-LR (MC-LR)去除率的影响.结果表明,单独H₂O₂对MC-LR基本无去除效果;单独UV工艺可以一定程度上降解MC-LR;而UV/H₂O₂联合工艺由于发生协同作用明显提高降解效率.试验发现,随着光强的增大,MC-LR的去除率不断提高;随着MC-LR初始浓度的增大,其去除率不断降低;随着H₂O₂投加量的增大,降解速率常数逐渐增大,当H₂O₂投加量由1 mmol/L增大到3 mmol/L时,降解速率常数由0.084 4上升到0.166 4;当pH为3.13时,在相同条件下MC-LR的去除效果最好;阴离子的投加不利于MC-LR的降解,其中CO^2-₃、NO^-₃影响最大.     

泥水预分离MBR膜污染缓减效能研究

通过长期运行实验,进行了泥水预分离膜生物反应器（sludge/water pre-separation membrane bioreactor, S/W-MBR）与传统淹没式膜生物反应器（submerged membrane bioreactor, SMBR）对比研究,考察了污泥浓度、胞外聚合物含量（extracellular polymeric substances, EPS）及过膜阻力（trans-membrane pressure, TMP）随运行时间的变化规律及其对膜污染的缓减作用.结果表明,S/W-MBR与SMBR生物区的污泥浓度基本一致,而S/W-MBR膜区的污泥浓度较SMBR有显著降低.两者生物区的EPS含量均随运行时间的延长而增加,而S/W-MBR膜区的单位质量污泥的EPS含量始终保持在15 mg/g左右的较低水平.S/W-MBR比SMBR具有更好的缓减膜污染能力,在近90d的连续运行过程中,前者的膜组件仅需清洗2次,后者的膜组件清洗了5次.     

碳源类型对A~2O系统脱氮除磷的影响

采用52.5 L的A2O反应器,以乙酸和丙酸分别作为进水唯一碳源,系统研究了进水碳源类型对脱氮除磷和代谢过程的影响.结果表明,在进水COD为250 mg/L左右,NH+4-N为52 mg/L左右的条件下,原水碳源类型对TN的去除影响不大,系统TN去除率均在65%左右.进水碳源类型对TP的去除及相应污泥中PHA的类型、含量和代谢及糖原的变化影响较大.乙酸为唯一碳源时,厌氧区放磷浓度较高,污泥中PHA的成分主要为PHB和PHV,两者在厌氧区的合成量差别不大,PHB在随后的反应过程中变化较大,对除磷代谢过程起主要作用,而PHV的变化较小.丙酸作为进水唯一碳源时,厌氧区的放磷浓度偏低,主要合成PHV,几乎不含PHB,PHV在随后吸磷过程中浓度变化较大,对除磷代谢起主要作用,而且出水TP浓度偏低.碳源类型对污泥中糖原的代谢也有影响,乙酸为碳源时糖原的含量高,变化范围也较大,丙酸为碳源时糖原的变化幅度较小.在同步脱氮除磷系统中,与乙酸相比,丙酸是一种更合适的碳源.