春季生物作用对山地岩溶池水地球化学特征的影响

岩溶水文系统对外界环境变化敏感,使得岩溶区水质存在昼夜、小时甚至分钟等尺度的变化.许多地表水体都会经历p H值、溶解性气体、微量元素以及其他水化学指标的昼夜变化.重庆金佛山水房泉及受其补给的水池地处海拔2 050 m的山地岩溶区,具有温带气候特征.通过对水房泉泉水(以下简称泉水)及水池进行为期3 d的昼夜监测,以期探究春季生物作用对岩溶池水地球化学的影响.研究发现,在昼夜时间尺度上,泉水地球化学指标基本稳定,未表现出昼夜变化,池水地球化学指标化学表现出了昼夜波动,但水温、溶解氧、p H值、电导率等物理化学指标昼夜变化幅度较小.在不同的天气条件下,水温、溶解氧、Cl-等昼夜变化幅度存在差别;池水二氧化碳分压(p CO2)、Ca2+、DIC白天降低、晚上升高,方解石饱和指数(SIc)相反;这些指标的变化受控于温度、碳酸盐岩矿物的溶解与沉淀、水生植物光合作用与呼吸作用;通过亨利常数的计算,发现水温变化对p CO2变化的影响仅占0.79%~10.01%,水温、碳酸盐岩沉淀等物理因素对DIC损失量的贡献率为39%,水生植物光合作用的贡献率为61%.     

不同湿地模型中根系微生物的多样性

为了研究不同植物和滤料组合的小型湿地模型在处理养殖池塘水体过程中根系微生物群落的特征,并分析植物对根系微生物富集的影响,本研究对两种植物(茭白和慈菇)和两种滤料(石榴石和磁铁矿)进行组合构建了6种不同的湿地模型,并利用高通量测序技术分析湿地植物根系微生物的结构特点和多样性.结果表明:不同湿地模型根系微生物的种类和数量各不相同;所有收集的微生物总体上属于52个门,118个纲,455科,905个属和1 426个种;根据Shannon指数,茭白(平均为5.77)比慈菇(平均为5.29)在微生物富集方面具有更强的能力;但是,慈菇和茭白根系微生物中变形菌门的比例分别平均为61.97%和51.78%,说明慈菇能够更好地富集变形菌.β-变形菌纲为实验期间不同植物根际富集的主要细菌类群.本研究结果为人工湿地植物优化选择提供了理论基础和湿地组合最佳构建提供了基础资料.     

Simultaneous removal of Cu(II) and Cr(VI) by Mg–Al–Cl layered double hydroxide and mechanism insight

Mg–Al–Cl layered double hydroxide (Cl-LDH) was prepared to simultaneously remove Cu(II) and Cr(VI) from aqueous solution. The coexisting Cu(II) (20 mg/L) and Cr(VI) (40 mg/L) were completely removed within 30 min by Cl-LDH in a dosage of 2.0 g/L; the removal rate of Cu(II) was accelerated in the presence of Cr(VI). Moreover, compared with the adsorption of single Cu(II) or Cr(VI), the adsorption capacities of Cl-LDH for Cu(II) and Cr(VI) can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu(II) (200 mg/L) and Cr(VI) (400 mg/L). The affecting factors (such as solution initial pH, adsorbent dosage, and contact time) have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg²⁺ and Al³⁺ in relevant solutions were monitored. To get the underlying mechanism, the Cl-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr(VI) with Cl⁻ in Cl-LDH interlayer, isomorphic substitution of Mg²⁺ with Cu²⁺, formation of Cu₂Cl(OH)₃ precipitation, and the adsorption of Cr(VI) by Cu₂Cl(OH)₃. This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by Cl-LDH.     

Capability of cation exchange technology to remove proven N-nitrosodimethylamine precursors

N-nitrosodimethylamine(NDMA) precursors consist of a positively charged dimethylamine group and a non-polar moiety, which inspired us to develop a targeted cation exchange technology to remove NDMA precursors. In this study, we tested the removal of two representative NDMA precursors, dimethylamine(DMA) and ranitidine(RNTD), by strong acidic cation exchange resin. The results showed that pH greatly affected the exchange efficiency, with high removal(DMA 78% and RNTD 94%) observed at pH pk_a-1 when the molar ratio of exchange capacity to precursor was 4. The exchange order was obtained as follows: Ca~(2+) Mg~(2+) RNTD~+ K~+ DMA~+ NH_4~+ Na~+. The partition coefficient of DMA~+to Na~+was 1.41 ± 0.26, while that of RNTD~+to Na~+was 12.1 ± 1.9. The pseudo second-order equation fitted the cation exchange kinetics well. Bivalent inorganic cations such as Ca~(2+)were found to have a notable effect on NA precursor removal in softening column test. Besides DMA and RNTD, cation exchange process also worked well for removing other 7 model NDMA precursors. Overall, NDMA precursor removal can be an added benefit of making use of cation exchange water softening processes.     

基于LiDAR、SRTM DEM的祁连山黑河流域十一冰川2000-2012年物质平衡估算

以祁连山黑河流域十一冰川为例,利用机载三维激光扫描数据（Light Detection And Ranging, LiDAR）和SRTM DEM数据,在LiDAR点云数据预处理、高程数据配准、校正、误差评估的基础上,建立基于大地测量法的冰川物质平衡计算流程。表明：2000-2012年十一冰川冰面高程变化为-7.47±0.92βm,变化率为-0.62±0.08 m·a^-1,估算十一冰川的年均物质平衡为 -0.53±0.07βm w.e.,累积物质平衡为-6.35±0.78βm w.e.,折合水当量约为（330.4±40.8）×10^4βm³;与其他典型监测冰川物质平衡进行对比和分析,论证了估算结果的可靠性;LiDAR数据具有非常高的精度和空间分辨率,目前关于其在冰川物质平衡研究中的应用很少,论文尝试将其应用于冰川物质平衡变化研究中,具有广阔的发展前景。     

复合生物阴极型微生物燃料电池处理废水及同步产电性能

为研究生物阴极在MFC（微生物燃料电池）中的应用,分别以粒径为2~4 mm的颗粒活性炭和粒径为2~4、4~8、8~12 mm的颗粒石墨为阴极基质材料,构建升流复合生物阴极型单室MFC,研究阴极基质材料的种类和粒径对MFC的产电性能和净水效能的影响.结果表明:当阳极基质材料为2~4 mm粒径的颗粒活性炭时,燃料电池中利用玻璃纤维取代离子交换膜,阴极基质材料为选用4~8 mm粒径颗粒石墨的反应柱产电量最大,为534 mV（外电阻为1 000 Ω）,最大功率密度达到631.6 mW/m3,库伦效率为3.82%;阴极的pH越低越有利于阴极的产电反应;不同阴极基质材料的MFC对COD_Cr去除率均在80%左右,TN、NH₄+-N及TP的去除率最高可分别达到79%、93%和34%.研究显示,阴极基质材料的种类和粒径对MFC的产电性影响较大,但对其净水效能的影响不大.      

Effect of MoO3 on vanadium based catalysts for the selective catalytic reduction of NOx with NH3 at low temperature

The selective catalytic reduction(SCR) activities of the MoO_3 doped V/WTi catalysts prepared by the incipient wetness impregnation method at low temperature were investigated.The results showed that the addition of MoO_3 could enhance the NO_ xconversion at low temperature and the best SCR activity was obtained when the dosage of MoO_3 reached5 wt.%. The NH3-TPD and DRIFTS experiments indicated that the addition of MoO_3 changed the type and number of acid sites on the surface of catalysts and reaction activities of acid sites were altered at the same time. The redox capacity and amount of active oxygen species got improved for V3Mo5/WTi catalyst, which could be confirmed by the H_2-TPR and transient response experiments. Water vapor inhibited the NO_xconversion at low temperature. Deposition of ammonium sulfate or bisulfate might be main reason for the loss of catalytic activity in the presence of SO_2 at low temperature. Choosing the suitable NH_3/NO ratio and elevation of reaction temperature both could weaken the influence of SO_2 on the SCR activity of the V3Mo5/WTi catalyst. Thermal treatment of the deactivated catalyst at350°C could get the low temperature activity recovered. The decrease of GHSV improved the de NO_x efficiency at low temperature and we speculated that the rational technological process and operation parameters could contribute to the application of this kind of catalysts in real industrial environment.     

Effects of free ammonia on volatile fatty acid accumulation and process performance in the anaerobic digestion of two typical bio-wastes

The effect of free ammonia on volatile fatty acid(VFA)accumulation and process instability was studied using a lab-scale anaerobic digester fed by two typical bio-wastes:fruit and vegetable waste(FVW)and food waste(FW)at 35°C with an organic loading rate(OLR)of 3.0 kg VS/(m~3·day). The inhibitory effects of free ammonia on methanogenesis were observed due to the low C/N ratio of each substrate(15.6 and 17.2,respectively). A high concentration of free ammonia inhibited methanogenesis resulting in the accumulation of VFAs and a low methane yield. In the inhibited state,acetate accumulated more quickly than propionate and was the main type of accumulated VFA. The co-accumulation of ammonia and VFAs led to an "inhibited steady state" and the ammonia was the main inhibitory substance that triggered the process perturbation. By statistical significance test and VFA fluctuation ratio analysis,the free ammonia inhibition threshold was identified as 45 mg/L. Moreover,propionate,iso-butyrate and valerate were determined to be the three most sensitive VFA parameters that were subject to ammonia inhibition.     

In-situ synthesis of TiO2 rutile/anatase heterostructure by DC magnetron sputtering at room temperature and thickness effect of outermost rutile layer on photocatalysis

TiO_2 rutile/anatase heterostructure thin films with varying rutile thickness have been in-situ synthesized via DC magnetron sputtering with Ar gas at room temperature. The crystal texture, surface morphology, energy gap and optical properties of the films have been investigated by X-ray diffraction meter, grazing incidence X-ray diffraction meter, Raman spectroscopy, scanning electron microscopy, and UV–visible spectrophotometer, which indicates that the rutile/anatase heterostructure films are successfully fabricated. The further degradation experiments display that the photocatalytic activity can be dramatically affected by the thickness of the outmost rutile layer and the 100 nm thickness exhibits the best performance in all of the TiO_2 thin films. With the increase of the outmost rutile layer, the optical band gap of TiO_2 film displays a systematic decrease slightly. However,the change in photocatalytic activity does not coincide with that in the band gap. The photoresponse and electrochemical properties of the thin films have been characterized to understand the mechanism of the varied photocatalytic activity.     

Effect of barium sulfate modification on the SO2 tolerance of V2O5 /TiO2 catalyst for NH3-SCR reaction

Sulfur poisoning of V_2O_5/BaSO_4–TiO_2(VBT),V_2O_5/WO_3–TiO_2(VWT) and V_2O_5/BaSO_4–WO_3–TiO_2(VBWT) catalysts was performed in wet air at 350℃ for 3 hr,and activities for the selective catalytic reduction of NO_x with NH_3 were evaluated for 200–500℃.The VBT catalyst showed higher NO_x conversions after sulfur poisoning than the other two catalysts.The introduction of barium sulfate contributed to strong acid sites for the as-received catalyst,and eliminated the redox cycle of active vanadium oxide to some extent,which resulted in a certain loss of activity.Readily decomposable sulfate species formed on VBT-S instead of inactive sulfates on VWT-S.These decomposable sulfates increased the number of strong acid sites significantly.Some sulfate species escaped during catalyst preparation and barium sulfate was reproduced during sulfur poisoning,which protects vanadia from sulfur oxide attachment to a great extent.Consequently,the VBT catalyst exhibited the best resistance to sulfur poisoning.