挥发性有机污染物排放控制标准制订中的关键技术问题研究

研究分析了挥发性有机污染物排放标准制订中4个关键技术问题:污染因子选择、控制指标确定、限值的确定以及技术管理措施.结果表明,应根据毒性和光化学反应性选择污染因子;确定控制指标应既考虑有组织控制指标,又考虑无组织的控制指标;确定排放限值应明确是基于控制技术还是基于健康风险;同时制定技术管理措施以通过源头和过程控制挥发性有机污染物排放.     

聚合氯化铁-聚(环氧氯丙烷-二甲胺)复合絮凝剂在模拟水处理中的混凝特性研究

制备出一系列具有不同聚合氯化铁(PFC)的碱化度(B)、不同聚(环氧氯丙烷-二甲胺)[P(EPI-DMA)]质量分数[ω(E)]和黏度(η)的PFC-P(EPI-DMA)复合混凝剂,并将其用于模拟染料废水和模拟天然地表水的絮凝脱色处理,对比探讨了ω(E)、η和B对PFC-P(EPI-DMA)中铁的形态分布及其混凝效果的影响,以及混凝作用机制.结果表明,复合絮凝剂中铁的有效形态含量随ω(E)的增大而不断降低;η=850 mPa.s时,复合混凝剂中铁的有效形态含量最高;随B值的增大,Feb含量先增大后减少,而Fec含量逐渐增大.一定程度上使用预水解程度较低、有机成分黏度较大的PFC-P(EPI-DMA)有利于混凝效果的提高,复合混凝剂中有机成分质量分数对混凝效果的影响则与处理对象有关.在模拟水处理中,复合混凝剂依靠电性中和及架桥吸附能力发挥混凝特性.     

杭州市典型企业废水中挥发性有机物排放特征及其评价

以10家杭州市典型企业进出口废水为调查对象,用顶空气相色谱质谱法测定77种挥发性有机物(VOCs),分析其排放特征,并对监测结果进行评价.结果表明,进口废水共定量检出22种VOCs,检出质量浓度范围为7~3.39×106μg·L-1;出口废水共定量检出14种VOCs,检出质量浓度范围为16~6.82×104μg·L-1.就行业而言,香精香料制造企业进出口废水VOCs检出的质量浓度最高.以《污水综合排放标准》(GB 8978-1996)三级排放标准为评价标准时,1号企业出口废水检出甲苯质量浓度为2.45×103μg·L-1,超过标准限值.以挥发性有机物的水介质排放环境目标值(DMEG WH)为标准时,3号企业出口废水检出的正丁醇、异丙醇、丙酮质量浓度均超过它们各自的水介质排放环境目标值.     

武汉市秸秆燃烧VOCs排放估算及管理对策

秸秆燃烧是我国人为源挥发性有机物(volatile organic compounds,VOCs)排放的重要来源之一,其排放对气候变化和人体健康都有很大影响.对该来源VOCs排放量的可靠估算是在区域或城市范围内进行排放效应分析和污染控制的重要前提.根据2005~2011年武汉市农作物的总产量,采用排放因子分析法估算了武汉市及主要6个农作物产区的秸秆燃烧VOCs的排放量,并分别计算其耕地排放强度(I c)和区域排放强度(I r).结果表明,武汉市2005~2011年年均秸秆燃烧VOCs排放量约为(3 163±139)t,I c和I r分别为(1.52±0.06)t·km-2和(0.37±0.02)t·km-2.粮食类和油料类农作物秸秆燃烧是主要的排放源,需优先控制7大类21种VOCs物质.武汉市分区VOCs排放量从大到小排序依次为黄陂区、新洲区、江夏区、蔡甸区、汉南区、东西湖区,前4个区的排放总量占到武汉市的近九成.江夏区、汉南区、黄陂区和新洲区应作为秸秆燃烧VOCs排放的优先控制区,尤其是能作为全国代表性的江夏区,应引起高度重视.在进行区域或城市范围的秸秆燃烧产生污染物质的生态风险评价时,该污染物的I c和I r都是需要考虑的重要基础数据.最后,提出大力发展农村秸秆资源综合循环经济利用是解决区域或城市范围内秸秆燃烧产生环境问题的可行之径.     

基于液相31P核磁共振(NMR)技术的巢湖沉积物中有机磷形态研究

利用改进的沉积物有机磷提取方法和液相31P核磁共振(NMR)分析方法,研究了巢湖表层沉积物有机磷形态.结果表明:西部湖区表层沉积物总磷含量高于东部湖区,其平均含量分别为(1089.82±108.14) mg·kg-1和(497.80±51.59) mg·kg-1;东部湖区沉积物中有机磷百分含量(31.88％±2.41％)高于西部湖区(20.86％±1.65％);表层沉积物主要磷份组成包括膦酸盐(Phon-P)、正磷酸盐(Ortho-P)、磷酸单酯(Mono-P)、磷脂(Lipid-P)、DNA(DNA-P)、焦磷酸盐(Pyro-P);磷酸单酯为有机磷的主要组分,平均含量占总磷的22.12％±5.32％;磷酸单酯和DNA百分含量东部湖区大于西部湖区,磷酸单酯百分含量分别为25.99％±2.29％和16.30％±1.06％,DNA百分含量分别为5.61％±0.24％和3.85％±1.01％.31P核磁共振技术可以有效的应用于巢湖等富营养化湖泊沉积物磷形态分析;巢湖表层沉积物以无机磷为主,有机磷种类丰富,以磷酸单酯为主.     

垦殖对湿地土壤有机碳垂直分布及可溶性有机碳截留的影响

通过测定和计算兴凯湖地区沼泽湿地及由其垦殖而来的旱田和水田土壤剖面有机碳含量和密度及土壤剖面不同深度土壤溶液中可溶性有机碳含量,分析了垦殖对兴凯湖周边沼泽湿地土壤有机碳垂直分布及土壤剖面截留可溶性有机碳的影响.结果表明,垦殖显著影响湿地0～40 cm土壤有机碳含量,大豆田和水稻田0～10、10～20、20～30、30～40 cm土壤有机碳含量与湿地相比分别降低了79.07%和82.01%、79.01%和82.28%、79.86%和92.90%、37.49%和78.05%;40 cm以下土层土壤有机碳含量垦殖前后差异不显著.大豆田和水稻田有机碳密度相比沼泽湿地分别降低了25.50%和47.35%,但三者1 m深土壤中大部分的有机碳均是储存在0～50 cm土层中.垦殖前后土壤有机碳含量与深度之间的关系均可用指数函数来描述,垦殖改变了土壤有机碳含量但并未改变其随土壤深度的变化规律.垦殖为大豆田土壤剖面对可溶性有机碳的截留效果较湿地和水稻田更明显,沼泽湿地和水稻田对可溶性有机碳的截留效果大致相当.     

Investigation of low-molecular weight organic acids and their spatiotemporal variation characteristics in Hongfeng Lake, China

The identities and concentrations of low-molecular-weight organic acids (LMWOAs) were determined by ion chromatography throughout a 20-m water column in Hongfeng Lake, China. The spatiotemporal variations of LMWOAs and their contributions to dissolved organic matter (DOM) in a research period of 24 hr were also investigated. The results demonstrated that five LMWOAs (lactic, acetic, pyruvic, sorbic, oxalic acid) were detected, and their total concentration and proportion in DOC were 6.55 μmol/L and 7.47%. Their average levels were 2.50, 0.65, 2.35, 0.96 and 0.09 μmol/L, respectively. LMWOAs were higher during daytime (10:00-18:00 on Jun 13, 2008) than nighttime (21:00-6:00 the next morning), in particular 4.99 μmol/L high in the epilimnion ( 1 m water depth), reflecting the fact that direct import from terrigenous sources and photochemical production from humic materials were dominant during LMWOAs’ origin and accumulation. The same factors caused LMWOAs to be 0.63 μmol/L in the epilimnion higher than in the hypolimnion. The rapid decrease of total organic acid (TOA) up until 18:00 mainly resulted from bio-uptake and mineralization in the hypolimnion (>1 m water depth). Pyruvic acid increased with time in the epilimnion and decreased in the hypolimnion, largely related to the two contrary processes of continuous degradation and synthesis of macromolecular organic matter during life materials’ cycle mediated by organisms. Simultaneously, plankton behavior and thermal stratification played a pivotal role in LMWOAs’ behavior in the water column, causing decreasing and increasing profiles. The distribution of LMWOAs represents an interesting resource for biogeochemical research of DOM in aquatic ecosystems.     

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.     

Influence of dissolved organic matter character on mercury incorporation by planktonic organisms：An experimental study using oligotrophic water from Patagonian lakes

Ligands present in dissolved organic matter （DOM） form complexes with inorganic divalent mercury （Hg^2＋） affecting its bioavailability in pelagic food webs. This investigation addresses the influence of a natural gradient of DOM present in Patagonian lakes on the bioaccumulation of Hg^2＋ （the prevailing mercury species in the water column of these lakes） by the algae Cryptomonas erosa and the zooplankters Brachionus calyciflorus and Boeckella antiqua. Hg^2＋ accumulation was studied through laboratory experiments using natural water of four oligotrophic Patagonian lakes amended with^197Hg^2＋. The bioavailability of Hg^2＋ was affected by the concentration and character of DOM. The entrance of Hg^2＋ into pelagic food webs occurs mostly through passive and active accumulation. The incorporation of Hg^2＋ by Cryptomonas, up to 27% of the Hg^2＋ amended, was found to be rapid and dominated by passive adsorption, and was greatest when low molecular weight compounds with protein-like or small phenolic signatures prevailed in the DOM. Conversely, high molecular weight compounds with a humic or fulvic signature kept Hg^2＋ in the dissolved phase, resulting in the lowest Hg^2＋ accumulation in this algae. In Brachionus and Boeckella the direct incorporation of Hg from the aqueous phase was up to 3% of the Hg^2＋ amended. The dietary incorporation of Hg^2＋ by Boeckella exceeded the direct absorption of this metal in natural water, and was remarkably similar to the Hg^2＋ adsorbed in their prey. Overall, DOM concentration and character affected the adsorption of Hg^2＋ by algae through competitive binding, while the incorporation of Hg^2＋ into the zooplankton was dominated by trophic or dietary transfer.     

Electrochemical and spectroscopic characteristics of dissolved organic matter in a forest soil profile

Dissolved organic matter （DOM） represents one of the most mobile and reactive organic compounds in ecosystem and plays an important role in the fate and transport of soil organic pollutants, nutrient cycling and more importantly global climate change. Electrochemical methods were first employed to evaluate DOM redox properties, and spectroscopic approaches were utilized to obtain information concerning its composition and structure. DOM was extracted from a forest soil profile with five horizons. Differential pulse voltammetry indicated that there were more redox-active moieties in the DOM from upper horizons than in that from lower horizons. Cyclic voltammetry further showed that these moieties were reversible in electron transfer. Chronoamperometry was employed to quantify the electron transfer capacity of DOM, including electron acceptor capacity and electron donor capacity, both of which decreased sharply with increasing depth. FT-IR, UV-Vis and fluorescence spectra results suggested that DOM from the upper horizons was enriched with aromatic and humic structures while that from the lower horizons was rich in aliphatic carbon, which supported the findings obtained by electrochemical approaches. Electrochemical approaches combined with spectroscopic methods were applied to evaluate the characteristics of DOM extracted along a forest soil profile. The electrochemical properties of DOM, which can be rapidly and simply obtained, provide insight into the migration and transformation of DOM along a soil profile and will aid in better understanding of the biogeochemical role of DOM in natural environments.