用EXAFS研究Zn在水锰矿上的吸附-解吸机理

用延展X光吸收精细结构光谱(EXAFS)研究了重金属Zn(Ⅱ)在水锰矿(γ-MnOOH)上吸附产物的微观结构及其吸附机理.结果表明,Zn(Ⅱ)-水锰矿体系中(pH 7.5,0.1mol/LNaNO₃介质,25℃),Zn²⁺主要是通过共用水合Zn²⁺的O原子及水锰矿表面上的O原子形成Zn-O键,从而结合到水锰矿固体表面上的.平均Zn-O原子间距为1.998±0.010 A(n=3).这个Zn-O键键长是六配位的Zn(H₂O)²⁺₆及其水解产物四配位的Zn(OH)₂或Zn(OH)₄^2-各以一定比例混合吸附于水锰矿表面而形成的.同时,对第二配位层(Zn-Mn相互作用)的EXAFS图谱分析证明存在2个典型的Zn-Mn原子间距,即R₁=3.08±0.024A(n=3)和R2=3.54±0.018 A(n=3).这2个Zn-Mn原子距分别对应于水锰矿结构单元MnO6八面体与Zn水合离子ZnO多面体结合的2种方式,即共用2个O原子的边-边结合与共用1个O原子的角-角结合.边-边结合是较强的吸附位,Zn-Mn原子距较短(R₁=3.08A),吸附较不可逆.角-角结合是较弱的吸附位,Zn-Mn原子距较长(R₂=3.54A),吸附较为可逆.这一结果从微观上证明了亚稳平衡态吸附理论(MEA理论)的基本假设,即具有相同吸附密度的同一吸附质由于吸附力强弱以及微观构型的不同可具有不同的化学位,因而证明了修正传统吸附热力学的基本假设(吸附密度为热力学状态函数)的必要性.宏观的吸附-解吸热力学实验表明Zn(Ⅱ)在水锰矿上的吸附是不可逆的,EXAFS结果指出这种不可逆性主要是由Zn水合离子中ZnO多面体与水锰矿结构单元MnO₆八面体之间的边-边结合所导致的.     

中国浏阳农村地区人群暴露参数

以湖南省浏阳市农村地区人群为研究对象,采用问卷调查的方式对研究地区人群的暴露参数进行研究,结果表明:研究地区成人男性、女性的平均体质量分别为62.45和53.71kg,平均体表面积分别为1.710和1.546m2;成人日均饮水摄入量为1428 mL,P₉₅(第95百分位数)为3350mL,其中,日均直接饮水量为1035mL,P₉₅为2500mL;调查地区大米、面粉、鱼类、猪肉、鸡肉、蛋类(鸡蛋和鸭蛋合计)日均摄入量,成人男性为335.54、89.28、15.41、18.48、14.18和21.70g/d,成人女性为269.28、68.45、14.89、16.73、13.11和18.07g/d. 研究还发现,调查地区人群饮用水源以泉水和井水为主,分别占52.42%和36.31%,也有个别人群饮用河水和湖水等地表水. 研究结果与美国和日本暴露参数推荐值相比有较大差异,与我国同类研究相比也存在一定的差异,说明暴露参数具有区域性、种族性等特征.      

超细水雾抑制煤燃烧的模拟实验研究

为了研究超细水雾对煤燃烧的抑制效果,基于小尺寸空间抑制燃烧实验平台,研究了超细水雾对煤燃烧的抑制效果,计算在超细水雾作用下实验空间内部氧气、二氧化碳、一氧化碳体积分数的变化情况以及燃烧空间内不同部位的温度变化情况,并且与煤自由燃烧的情况做对比。研究表明超细水雾对煤燃烧的火灾发展过程有很好的抑制作用。研究结论对超细水雾应用于熄灭矿井煤炭火灾具有一定的指导意义     

辛置煤矿水力压裂卸压增透影响半径数值模拟研究

随着开采深度的增加,辛置煤矿瓦斯涌出量显著增大。为了提高瓦斯抽采效率,拟采用水力压裂卸压增透技术。理论分析了水力压裂对煤层的卸压增透作用,基于此利用RFPA模拟软件对辛置煤矿2-559回采工作面水力压裂卸压增透进行了数值模拟。研究表明,水力压裂主要在以下3个方面对煤体起到增透作用:使煤体卸压、提高煤层透气性;湿润煤体,增加塑性;改善瓦斯抽放环境。辛置煤矿2-559回采工作面水力压裂所需压力约为15MPa,压裂半径为5-6m,以此可以初步确定现场施工过程中水力压裂钻孔间距以不大于10m为宜。     

基于模拟植物生长算法的快线公共车辆优化调度研究

公共车辆的运营优化调度能够很好的减少城市交通拥堵,缓解交通压力,保证多方面的利益。对乘客高峰期快线公共车辆的调度进行了研究。首先运用了三元组α/β/γ方法对问题进行了描述,将乘客高峰期快线车辆的调度描述为一类以最小化制造期和平均等待时间为目标,具有先入先出原则和机器适用限制的流水车间动态调度问题。并在此基础上建立了相应的数学模型;接着,运用模拟植物生长算法进行了算法设计;最后,用实际数据进行了数值仿真,结果证明该研究具有较高的理论及现实价值。     

Effects of sepiolite and biochar on microbial diversity in acid red soil from southern China

Sepiolite and biochar can immobilize heavy metals and organic pollutants in soil effectively, but their impact on the soil microbial community and diversity is still unclear. High-throughput Illumina MiSeq method was used to study the effects of sepiolite and biochar on the diversity of microbial communities in acid red soil amended with cadmium and atrazine. A total of 47,472 microbiological Operational Taxonomic Units (OTUs) were found in all the treated soil samples. Sepiolite and biochar enriched the diversity of soil microbes at different classification levels and OTUs, but the effect of biochar was stronger than that of sepiolite. A Venn diagram showed that compared with other treatments, adding 2% biochar could promote the growth of specific microbes, which is better than the case for 5% biochar. The heat map of species abundance cluster showed that the dominant microbes in soil were different for different treatment doses of sepiolite and biochar. Among all the soil treatments, the top ten dominant bacterial phyla (from high to low dominance) were: Actinobacteria, Proteobacteria, Firmicutes, Bacteroidetes, Acidobacteria, Gemmatimonadetes, Chloroflexi, Planctomycetes, Cyanobacteria­, and Verrucomicrobia. The addition of sepiolite and biochar promoted the restoration of the microbial community diversity in contaminated soil.     

Biodegradability of organic substances by ATP test

The aerobic biodegradability of organic substances in water is characterized by determination of energy change ‐ ATP content in microbial cells during biodegradation. A satisfactory result is obtained under the following conditions: the initial concentration of tested substance is 100mg/l (as DOC), the amount of the inoculum in the biological medium is 500mg/l (as MLSS), and the duration of test time is 14 days. The evaluating system (peak time, peak height and IA index) is proposed to assess the biodegradability of 46 organic compounds and 7 wastewaters.     

Gridded usage inventories of chlordane in China

Chlordane (1,2,4,5,6,7,8,8-octachloro-3a,4,7, 7a-tetra-hydro-4,7-methanoindane) is one of organochlorine pesticides (OCPs) which has been listed as one of the persistent organic pollutants (POPs) to be reduced and finally eliminated in the Stockholm Convention on Persistent Organic Pollutants, because of its great persistence, toxicity, bio-accumulation and long-range transport potential. It is critical to create a national chlordane usage inventories for China to compile chlordane emission inventories, which is helpful for carrying out risk assessments and other researches related to chlordane in China. The annual data of chlordane usage was calculated and modified in accordance with the reported annual production of chlordane which was caculated on the basis of the termite distribution, the data of chlordane usage rate and the annual new construction area (NCA).With the help of Geographic Information System, the usage data of this NCA were allocated to a grid system then, with a 1/4° longitude by 1/6° latitude resolution and a size for each grid cell of approximately 25 km by 25 km. Between 1988 and 2008, the total usage of chlordane in China was 2745 t, accounting for approximately 80% of the production in the same period. Zhejiang Province was the largest consumer of chlordane in China, whose usage adds up to 980 t, greatly exceeding other provinces/regions, followed by Jiangsu Province (534 t) and Sichuan Province (428 t). The region with the least usage of chlordane was Beijing. Provinces of Guizhou, Henan and Hebei did not use any chlordane, even though termites had occurred in these provinces. Gridded usage inventories showed that the intensive use of chlordane was concentrated in the southeast part of China, Yangtze River Delta and Pearl River Delta in particular. The satisfaction of the inventories was supported by the consistence between the estimated data of annual usage and the reported annual production of chlordane, and by the consistence between distribution pattern of chlordane’s usage and ambient air concentration.     

Emission factors of gaseous carbonaceous species from residential combustion of coal and crop residue briquettes

Experiments were performed to measure the emission factors (EFs) of gaseous carbonaceous species, such as CO₂, CO, CH₄, and non-methane volatile organic compounds (NMVOCs), from the combustion of five types of coal of varying organic maturity and two types of biomass briquettes under residential burning conditions. Samples were collected in stainless steel canisters and 2,4-dinitrophenylhydrazine (DNPH) cartridges and were analyzed by GC-FID/MS and HPLC, respectively. The EFs from crop residue briquette burning were generally higher than those from coals, with the exception of CO₂. The dominant NMVOC species identified in coal smoke were carbonyls (41.7%), followed by C2 unsaturated hydrocarbons (29.1%) and aromatics (12.1%), while C2 unsaturated hydrocarbons were the dominant species (68.9%) emitted from the combustion of crop residue briquettes, followed by aromatics (14.4%). A comparison of burning normal crop residues in stoves and the open field indicated that briquettes emitted a larger proportion of ethene and acetylene. Both combustion efficiency and coal organic maturity had a significant impact on NMVOC EFs from burning coal: NMVOC emissions increased with increasing coal organic maturity but decreased as the combustion efficiency improved. Emissions from the combustion of crop residue briquettes from stoves occurred mainly during the smoldering process, with low combustion efficiency. Therefore, an improved stove design to allow higher combustion efficiency would be beneficial for reducing emissions of carbonaceous air pollutants.     

One-pot preparation of graphene oxide magnetic nanocomposites for the removal of tetrabromobisphenol A

A simple solvothermal method was used to prepare monodisperse magnetite (Fe₃O₄) nanoparticles attached onto graphene oxide (GO) sheets as adsorbents to remove tetrabromobisphenol A (TBBPA) from an aqueous solution. These Fe₃O₄/GO (MGO) nanocomposites were characterized by transmission electron microscopy. The adsorption capacity at different initial pH, contact duration, and temperature were evaluated. The kinetics of adsorption was found to fit the pseudo-second-order model perfectly. The adsorption isotherm well fitted the Langmuir model, and the theoretical maximum of adsorption capacity calculated by the Langmuir model was 27.26 mg?g^-1. The adsorption thermodynamics of TBBPA on the MGO nanocomposites was determined at 303 K, 313 K, and 323 K, respectively. The results indicated that the adsorption was spontaneous and endothermic. The MGO nanocomposites were conveniently separated from the media by an external magnetic field within several seconds, and then regenerated in 0.2 M NaOH solution. Thus, the MGO nanocomposites are a promising candidate for TBBPA removal from wastewater.