利用厌氧菌发酵产物处理含铅废水及机理研究

针对传统方法去除废水中重金属铅的缺陷,利用4株厌氧微生物的发酵产物,在不同投加量、pH、温度和反应时间下研究该产物的除铅效果。通过正交实验确定了微生物发酵产物对含铅废水处理的最佳反应条件为:发酵产物投加量为0.5 g,反应时间为20 min,pH=6,温度20℃,铅的去除率99.4%以上,并用蓄电池厂的实际废水进行验证实验,获得相同的效果;同时通过扫描电子显微镜和X-射线能量散射光谱分析厌氧细菌代谢的混合物成分,对去除机理进行了初步探讨,为生物技术处理含铅废水提供了一种新方法和理论依据。     

Fluorescence of sediment humic substance and its effect on the sorption of selected endocrine disruptors

Humic substances (HS) have a critical influence on the sorption of organic contaminants by soils and sediments. This paper describes investigations into the sorption behavior of three representative endocrine disruptors, bisphenol A (BPA), 17beta-estradiol (E2), and 17alpha-ethynylestradiol (EE2), onto sediments and HS extracted sediments using a batch technique. The organic carbon-normalized partition coefficients (K(oc)) for the extracted HS (K(oc)(hs)) were calculated, and the fluorescence spectra of the HS extraced from different sediment samples were gained using excitation/emission matrix (EEM). Particular attention was paid to the correlations between the fluorescence characteristics of HS and the log K(oc)(hs) of selected endocrine disruptors. The results show that the log K(oc)(hs) values range from 3.14 to 4.09 for BPA, from 3.47 to 4.33 for E2, and from 3.65 to 4.32 for EE2. Two characteristic excitation-emission peaks were observed for HS samples extracted from sediments. They are located at Ex/Em=250-260 nm/400-450 nm (peak alpha') and Ex/Em=310-330 nm/390-400 nm (peak alpha) respectively. The alpha' and alpha peak relative intensities I(alpha')/I(alpha) vary from 0.46 to 1.64 for different extracted HS samples. The similarity between fulvic acids (FA) Ex/Em pairs and those observed for HS indicates that FA is the predominant fraction of HS extracted from sediments. Moreover, the log K(oc)(hs) values of BPA, E2, and EE2 have a negative linear correlation to I(alpha')/I(alpha) values. Peak alpha is often attributed to relatively stable and high molecular weight aromatic fulvic-like matter. Therefore, the result presented here reveals that the abundance of aromatic rings in HS molecular structure plays a critical role in the sorption of selected endocrine disruptors.     

Modeling transport and fate of nitrogen from urea applied to a near-trench paddy field

A simple but comprehensive model is developed to quantify N losses from urea applied to a near-trench paddy field, considering all the N-transformations such as urea hydrolysis, volatilization, nitrification, denitrification, and all the important transportations like runoff, lateral seepage, vertical leaching and crop uptake. Seasonal average data of field observations for three crop seasons were used for model calibration and validation, which showed that ammonia volatilization accounted for 26.5-29.4% of the applied N and N uptake by crop occupied 38.2-44.8%, while N losses via surface runoff, vertical leaching and lateral seepage varied from 5.6-7.7%, 4.0-4.9% to 5.0-5.3% of the applied N, respectively. These observed results were well predicted by our model, indicating that the model performed effectively at quantifying N losses via individual processes in a wide range of urea application rates and benefit for developing water and fertilizer management strategies for near-trench paddy fields.     

城市污水厂污泥倾倒对海洋生物的毒性研究

以广州市和佛山市的5个城市污水处理厂的污泥为实验对象,选取费氏弧菌、蒙古裸腹溞、卤虫、裸项栉鰕虎鱼仔鱼4种不同营养级的海洋生物为受试对象,结合化学分析方法,研究广州区域周边污水污泥浸出液的生物毒性效应。结果显示各污水污泥浸出液的毒性均较大,且浸出液的Cu污染浓度较高;广州市污水污泥对4种受试生物的毒性效应要高于佛山市。从污泥毒性对受试生物的选择性方面分析,发现卤虫筛分能力强且灵敏度高,而费氏弧菌则相关性好且方法简捷。研究结果为反映城市污泥的生物毒性强度和选择合适毒性评价受试生物提供基础数据。     

Electrochemical oxidation of nitrogen-heterocyclic compounds at boron-doped diamond electrode

Nitrogen-heterocyclic compounds (NHCs) are toxic and bio-refractory contaminants widely spread in environment. This study investigated electrochemical degradation of NHCs at boron-doped diamond (BDD) anode with particular attention to the effect of different number and position of nitrogen atoms in molecular structure. Five classical NHCs with similar structures including indole (ID), quinoline (QL), isoquinoline (IQL), benzotriazole (BT) and benzimidazole (BM) were selected as the target compounds. Results of bulk electrolysis showed that degradation of all NHCs was fit to a pseudo first-order equation. The five compounds were degraded with the following sequence: ID > QL > IQL > BT > BM in terms of their rates of oxidation. Quantum chemical calculation was combined with experimental results to describe the degradation character of NHCs at BDD anode. A linear relationship between degradation rate and delocalization energy was observed, which demonstrated that electronic charge was redistributed through the conjugation system and accumulated at the active sites under the attack of hydroxyl radicals produced at BDD anode. Moreover, atom charge was calculated by semi empirical PM3 method and active sites of NHCs were identified respectively. Analysis of intermediates by GC-MS showed agreement with calculation results.     

Volatile organic compounds at swine facilities: A critical review

Volatile organic compounds (VOCs) are regulated aerial pollutants that have environmental and health concerns. Swine operations produce and emit a complex mixture of VOCs with a wide range of molecular weights and a variety of physicochemical properties. Significant progress has been made in this area since the first experiment on VOCs at a swine facility in the early 1960s. A total of 47 research institutions in 15 North American, European, and Asian countries contributed to an increasing number of scientific publications. Nearly half of the research papers were published by U.S. institutions.Investigated major VOC sources included air inside swine barns, in headspaces of manure storages and composts, in open atmosphere above swine wastewater, and surrounding swine farms. They also included liquid swine manure and wastewater, and dusts inside and outside swine barns. Most of the sample analyses have been focusing on identification of VOC compounds and their relationship with odors. More than 500 VOCs have been identified. About 60% and 10% of the studies contributed to the quantification of VOC concentrations and emissions, respectively. The largest numbers of VOC compounds with reported concentrations in a single experimental study were 82 in air, 36 in manure, and 34 in dust samples.The relatively abundant VOC compounds that were quantified in at least two independent studies included acetic acid, butanoic acid (butyric acid), dimethyl disulfide, dimethyl sulfide, iso-valeric, p-cresol, propionic acid, skatole, trimethyl amine, and valeric acid in air. They included acetic acid, p-cresol, iso-butyric acid, butyric acid, indole, phenol, propionic acid, iso-valeric acid, and skatole in manure. In dust samples, they were acetic acid, propionic acid, butyric acid, valeric acid, p-cresol, hexanal, and decanal. Swine facility VOCs were preferentially bound to smaller-size dusts.Identification and quantification of VOCs were restricted by using instruments based on gas Chromatography (GC) and liquid chromatography (LC) with different detectors most of which require time-consuming procedures to obtain results. Various methodologies and technologies in sampling, sample preparation, and sample analysis have been used. Only four publications reported using GC based analyzers and PTR-MS (proton-transfer-reaction mass spectrometry) that allowed continuous VOC measurement. Because of this, the majority of experimental studies were only performed on limited numbers of air, manure, or dust samples. Many aerial VOCs had concentrations that were too low to be identified by the GC peaks.Although VOCs emitted from swine facilities have environmental concerns, only a few studies investigated VOC emission rates, which ranged from 3.0 to 176.5 mg d⁻¹ kg⁻¹ pig at swine finishing barns and from 2.3 to 45.2 g d⁻¹ m⁻² at manure storages. Similar to the other pollutants, spatial and temporal variations of aerial VOC concentrations and emissions existed and were significantly affected by manure management systems, barn structural designs, and ventilation rates.Scientific research in this area has been mainly driven by odor nuisance, instead of environment or health concerns. Compared with other aerial pollutants in animal agriculture, the current scientific knowledge about VOCs at swine facilities is still very limited and far from sufficient to develop reliable emission factors.     

负载型金属催化剂的制备及印染废水的催化氧化处理

采用浸渍沉淀法制备负载型金属催化剂,考察了载体种类、活性组分种类、活性组分配比（n（Fe2+）∶n（Mn2+））、浸渍液浓度（以Mn2+计）、煅烧温度和煅烧时间对催化剂性能的影响。实验结果表明：活性炭负载FexOy-MnOx型催化剂具有较高的活性;将在浸渍液浓度0.5 mol/L（以Mn2+计）、n（Fe2+）∶n（Mn2+）=1∶2、煅烧温度250 ℃,煅烧时间8 h条件下制备的催化剂用于印染废水（COD=584 mg/L、色度500倍）的处理,在臭氧流量0.8 L/min、废水pH 7、催化剂加入量40 g/L、反应时间60 min的条件下,印染废水COD的去除率为83.2%;该催化剂具有良好的稳定性,连续使用6次后的COD去除率仍可达到61.1%。     

The mitigating effect of calcification-dependent of utilization of inorganic carbon of Chara vulgaris Linn on NH4-N toxicity

Increased ammonium (NH₄-N) concentrations in water bodies have been reported to adversely affect the dominant species of submersed vegetation in meso-eutrophic waters worldwide. However calcareous plants were lowly sensitive to NH₄-N toxicity.     

Roles of pyrolysis on availability,species and distribution of Cu and Zn in the swine manure: Chemical extractions and high-energy synchrotron analyses

Animal manures generally contain high levels of heavy metals that may pose a significant threat to soil and groundwater qualities. Pyrolysis as means of reducing metal availability in such feed stocks is recently encouraged, but systematic studies are currently lacking. The aim of this study was to assess the impact of pyrolysis temperature on the availability of Cu and Zn by chemical extraction, to determine the speciation of Cu and Zn by synchrotron-based X-ray spectroscopy, and finally to investigate the phase distribution of metal species in the carbonaceous materials by combining acid–base extractions and absorption spectroscopy data. The results showed that both Cu and Zn in the swine manure were mainly bound to organic functional groups. Cu (II) reduction and Cu (I)–S complexes were observed during the pyrolysis process. Zn species resembling ZnAc₂ was still dominant, being 60.8–69.2%, and ZnS increased by 6.6–21.8% in the carbonaceous materials. The distribution of Cu and Zn in the mineral, carbonized and non-carbonized organic phases varied greatly with the pyrolysis temperature. The higher the temperature, the more the metals existed in the mineral phase and carbonized organic phase. The decrease of EDTA extractable Cu and Zn with pyrolysis temperature was due to the increase of metals in the carbonized organic phase and mineral phase. It is suggested that pyrolysis at the relatively higher temperature is a better choice for metal-containing manure according to the metal speciation, solubility and availability.     

Dioxins and their fingerprint in size-classified fly ash fractions from municipal solid waste incinerators in China--mechanical grate and fluidized bed units

The distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), in brief dioxins, has seldom been addressed systematically in fly ash from municipal solid waste incinerators (MSWIs). This study shows the amount and fingerprint of PCDD/Fs in fly ash from four different Chinese MSWIs, that is, three mechanical grate units and one circulating fluidized bed unit. In these fly ash samples, dioxins-related parameters (international toxic equivalent quantity, total amount of PCDD/Fs, individual isomer classes, and 17 toxic 2,3,7,8-substituted congeners) all tend to increase with decreasing particle size for mechanical grate incinerators, yet only for the finest fraction for fluidized bed units. Moreover, the fluidized bed incinerator seems superior to grate incineration in controlling dioxins, yet a comparison is hampered by internal differences in the sample, for example, the fluidized bed fly ash has much lower carbon and chlorine contents. In addition, the presence of sulfur from mixing coal as supplemental fuel to the MSW may poison the catalytic steps in dioxins formation and thus suppress the formation of dioxins. With more residual carbon and chlorine in the fly ash, it is easier to form dioxins during cooling. Nevertheless, there is no apparent relation between Fe, Cu, and Zn contents and that of dioxins in fly ash.